KR101446824B1 - Optical anisotropic film and liquid crystal display device - Google Patents

Abstract

An optically anisotropic film which expresses a nematic phase or a Smectic phase and contains at least one kind of liquid crystal compound having birefringence Δn (λ) at a wavelength (λ) of the liquid crystal phase satisfying the following expression (1) An optically anisotropic film in which molecules of the liquid crystal compound are fixed in an oblique alignment state in an anisotropic film.

DELTA n (450 nm) / DELTA n (550 nm) < 1

Optically anisotropic film, liquid crystal compound, optical compensation, liquid crystal display

Description

Technical Field [0001] The present invention relates to an optically anisotropic film and a liquid crystal display,

INDUSTRIAL APPLICABILITY The present invention can be applied to a liquid crystal display device such as a reflection transmission type transflective type liquid crystal display device used for various displays such as an OA device, a portable game device, a cellular phone, and a portable terminal and optical compensation of the liquid crystal display device To an optically anisotropic film.

The liquid crystal display device is largely classified into three types: a transmissive type capable of displaying an image in a transmissive mode, a reflective type capable of displaying an image in a reflective mode, a transmissive mode and a reflective transmissive type capable of displaying an image in both reflective modes, And light weight, it has become widely used as a display device for a notebook computer, a television, and the like. Particularly, the reflective transmissive type liquid crystal display device adopts a reflective display mode and a transmissive display mode. By switching to a display mode depending on the ambient brightness, it is possible to perform clear display in a bright place or in a dark place while reducing power consumption , And various portable electronic devices.

The basic structure of a reflective transmission type liquid crystal display device is disclosed in, for example, Patent Documents 1 and 2 below.

The reflective transmissive liquid crystal display device has a problem that the number of the retardation layers is larger than that of the reflective liquid crystal display device and the transmissive liquid crystal display and the cost is increased and the cell thickness is increased. Further, since the retardation plates such as the? / 4 plate and the? / 2 plate used do not satisfy the performance in the visible light range, there is a problem with respect to the viewing angle characteristics such as occurrence of coloring and narrow viewing angle in the transmission mode .

As a method for enlarging the contrast viewing angle of the transmissive display, there has been proposed a method of using an optical compensatory film in which the nematic hybrid orientation is fixed on the? / 4 layer of the retardation film on both the upper and lower sides of the panel or on the? / 4 layer of one retardation film It has been practically used. For example, in Patent Documents 3 to 6 below.

A method of arranging a retardation film in a reflection area inside the panel for the purpose of reducing the number of retardation plates has been proposed (Patent Document 7). Also, for the purpose of improving the luminance of the transmission mode, particularly the peak luminance, a method of arranging the retardation film in the reflection region inside the panel has also been proposed (Patent Documents 8 to 14). For the same purpose of improving the peak luminance, a method of disposing a retardation film in the transmissive region inside the panel has been proposed (Patent Document 15). However, it is very difficult to ensure uniformity during production and to reduce light scattering. There has been a problem that it is difficult to increase the contrast viewing angle and the light utilization efficiency in the transmission mode.

Patent Document 1: JP-A-2000-29010

Patent Document 2: JP-A 2000-35570

Patent Document 3: JP-A-2002-31717

Patent Document 4: JP-A-2004-157453

Patent Document 5: JP-A-2005-62672

Patent Document 6: JP-A-2005-62670

Patent Document 7: JP-A-2003-322857

Patent Document 8: JP-A-2004-38205

Patent Document 9: JP-A-2004-219553

Patent Document 10: JP-A-2004-226829

Patent Document 11: JP-A-2004-226830

Patent Document 12: JP-A-2005-242031

Patent Document 13: JP-A-2005-283850

Patent Document 14: JP-A-2005-283851

Patent Document 15: JP-A-2004-145327

DISCLOSURE OF INVENTION

Problems to be solved by the invention

An object of the present invention is to provide a novel optically anisotropic film that can contribute to the improvement of the viewing angle characteristics of a liquid crystal display device, particularly a transflective liquid crystal display device, and which is easy to manufacture.

It is another object of the present invention to provide a liquid crystal display device capable of displaying a high luminance and a wide viewing angle and being easy to manufacture.

Means for solving the problem

Means for solving the above problems are as follows.

[1] An optically anisotropic film containing at least one liquid crystal compound that expresses a nematic phase or a Smectic phase and has birefringence Δn (λ) at a wavelength (λ) on the liquid crystal phase satisfies the following formula (1) An optically anisotropic film in which molecules of the liquid crystal compound in the optically anisotropic film are fixed in an oblique alignment state:

(1)? N (450 nm) /? N (550 nm) <1.

[2] An optically anisotropic film according to [1], wherein the angle of inclination of the molecule of the liquid crystal compound is different between the upper surface and the lower surface of the optically anisotropic film, and the average inclination angle of molecules of the liquid crystal compound is 5 ° to 85 °.

[3] The optically anisotropic film according to [1], wherein the angle of inclination of the molecules of the liquid crystal compound is the same at the upper and lower surfaces of the optically anisotropic film, and the average inclination angle of molecules of the liquid crystal compound is 5 ° to 85 °.

[4] The optically anisotropic film according to any one of [1] to [3], wherein the liquid crystal compound is a compound represented by the following general formula (I)

[Chemical Formula 1]

The compound of formula (I)

Wherein A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -NR- (R represents a hydrogen atom or a substituent), -S-, and -CO-; Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16 and forms a 5 or 6-membered ring together with the described CC = CC or C = CC = C in the formula ; R ¹ , R ² and R ³ each independently represent a substituent; m is an integer of 0 to 4; L ¹ and L ² each independently represent a single bond or a divalent linking group; X represents a nonmetal atom of Groups 14 to 16, wherein X may be a hydrogen atom or a substituent R ⁴ ; At least one of R, R ¹ , R ² , R ³ and R ⁴ has a polymerizable group.

[5] The optically anisotropic film according to [4], wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II)

(2)

In general formula (II)

In the formulas, A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -NR- (R represents a hydrogen atom or a substituent), -S-, and -CO-; Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16 and forms a 5 or 6-membered ring together with the described CC = CC or C = CC = C in the formula ; R ¹ , R ² , and R ³ each independently represent a substituent; m is an integer of 0 to 4; L ¹ and L ² each independently represent a single bond or a divalent linking group; R ⁵ and R ⁶ each independently represents a substituent, and at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ has a polymerizable group.

[6] The optically anisotropic film according to any one of [1] to [5], wherein the in-plane retardation (Re) is 80 to 160 nm at a wavelength of 550 nm.

[7] An optically anisotropic film according to any one of [1] to [6], which is formed by discharging a liquid containing at least the liquid crystal compound from a discharge head of an ink jet type onto a surface thereof and drying the liquid to form a liquid crystal phase, .

[8] A liquid crystal display device comprising a first optically anisotropic layer comprising any one of the optically anisotropic films [1] to [7], a backlight, a polarizing layer, a pair of substrates and a liquid crystal layer between the pair of substrates, And a liquid crystal cell having a reflective portion and a transmissive portion.

[9] The liquid crystal display of [8], wherein the first optically anisotropic layer is disposed between any one of the polarizing layer and the pair of substrates.

[10] The liquid crystal display of [8], wherein the first optically anisotropic layer is disposed between the pair of substrates.

[11] A retardation film having a retardation (Rth) in the thickness direction at a wavelength of 550 nm of 40 nm to 150 nm and a retardation (Re) of 0 nm to 20 nm at a wavelength of 550 nm, Wherein the second optically anisotropic layer is disposed at a position between the liquid crystal layer and the first optically anisotropic layer or at a position where the liquid crystal layer sandwiches the first optically anisotropic layer, 10].

[12] A liquid crystal display device according to [11], wherein Rth of the second optically-anisotropic layer exhibits a forward scatter wavelength dependency in a visible light range.

[13] The liquid crystal display device according to any one of [8] to [12], wherein the liquid crystal layer has a tilt angle of the liquid crystal in a black display state rather than a white display state.

[14] The liquid crystal display device according to any one of [1] to [14], wherein the average direction of the axis of the liquid crystal molecules in the liquid crystal layer at the time of black display is projected on the layer parallel surface and the direction in which the director of the molecules of the liquid crystal compound in the first optically anisotropic layer is projected onto the layer parallel surface The liquid crystal display device according to any one of [8] to [13].

Effects of the Invention

According to the present invention, it is possible to provide a novel optically anisotropic film which can contribute to the improvement of viewing angle characteristics of a liquid crystal display device, particularly a transflective liquid crystal display device, and which is easy to manufacture.

Further, according to the present invention, it is possible to provide a liquid crystal display device which is capable of displaying a high luminance and a wide viewing angle in a transmissive mode, and which is easy to manufacture, in a transflective liquid crystal display device capable of both reflective display and transmissive display have.

In addition, in the liquid crystal display device of the present invention, the retardation film used for the backlight side is not required in the conventional transreflective liquid crystal display device, which is effective in reducing the cost.

Embodiments of the Invention

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, the numerical range indicated by &quot; to &quot; means a range including numerical values before and after "to" as a lower limit value and an upper limit value. The terms &quot; orthogonal &quot; and &quot; parallel &quot; refer to a range of an exact angle of +/- 10 DEG with respect to an angle, and &quot; .

In the present invention, the term &quot; tilt angle &quot; refers to the angle formed by the inclined liquid crystal with the layer plane, and the maximum angle of the angle of the maximum refractive index with respect to the layer plane in the refractive index ellipsoid of liquid crystalline molecules . Thus, in a rod-shaped liquid crystalline molecule having positive optical anisotropy, the tilt angle means an angle formed by the direction of the major axis of the rod-shaped liquid crystalline molecule, that is, the director direction and the layer plane. In the present invention, the "average tilt angle" means the tilt angle on the upper surface of the retardation layer and the average value of the tilt angle on the lower plane. Therefore, in the uniformly inclined orientation, the average tilt angle in the layer coincides with the tilt angle of the upper surface and the tilt angle of the lower surface in the hybrid alignment, and the tilt angle of the upper surface and the tilt angle of the lower surface.

In the present specification, Re (?) And Rth (?) Indicate retardation in the plane and retardation in the thickness direction at the wavelength (?), Respectively. Re (?) Is measured by introducing light having a wavelength of? Nm in the direction of the film normal in KOBRA 21ADH or WR (trade name, manufactured by Ohji Instruments Co., Ltd.).

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (?) Is calculated by the following method.

Rth (λ) is a value obtained by dividing Re (λ) by the inclination axis (rotation axis) of the in-plane slow axis (determined by KOBRA 21ADH or WR) (in the case where there is no slow axis, The light beam having a wavelength of? Nm is incident from the oblique direction at a step of 10 degrees from the normal direction to the normal direction with respect to the film normal direction and six points are measured at all, and the measured retardation value and the average refractive index Based on the assumed value and the entered film thickness value, it is calculated in KOBRA 21ADH or WR.

In the above case, in the case of a film having a slow axis in the plane as a rotation axis from the normal direction and a direction in which the value of the retardation becomes zero at a certain tilt angle, the retardation value at an inclination angle larger than the tilt angle, Is calculated in KOBRA 21ADH or WR after it is changed to negative.

Further, the retardation value is measured from arbitrary oblique directions by using the slow axis as a tilting axis (rotation axis) (in a case where there is no slow axis, an arbitrary direction in the film plane is taken as the rotation axis) Based on the assumed value and the input film thickness value, Rth may be calculated by the following equations (7) and (8).

Equation (11)

Equation (12)

In the formula, Re (&amp;thetas;) represents the retardation value in the inclined direction from the normal direction. nx represents the index of refraction in the direction of the slow axis in the plane, ny represents the index of refraction in the direction orthogonal to nx in the surface, and nz represents the index of refraction in the direction perpendicular to nx and ny. and d represents the film thickness of the film.

In the case of a film in which the film to be measured can not be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film without an optical axis (OPTIC AXIS), Rth (?) Is calculated by the following method.

Rth (?) Is a value obtained by dividing Re (?) By 10 degrees (-50 degrees to +50 degrees) with respect to the normal direction of the film, with the slow axis in the plane (determined by KOBRA 21ADH or WR) , The light having a wavelength of? Nm is incident from the oblique direction, and 11 points are measured. Based on the measured retardation value and the assumed value of the average refractive index and the input film thickness value, it is calculated by KOBRA 21ADH or WR .

In the above measurement, a value of the catalog of various polymer films (JOHN WILEY & SONS, INC) and various optical films can be used as the assumption of the average refractive index. The value of the average refractive index can be measured with an Abbe refractometer if it is not already known. The values of the average refractive index of the main optical film are illustrated below; Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) and polystyrene (1.59). Nx, ny, and nz are calculated in KOBRA 21ADH or WR by inputting the assumptions of the average refractive index and the film thickness. Nz = (nx-nz) / (nx-ny) is further calculated by the calculated nx, ny, and nz.

[Optical anisotropic film]

The present invention relates to a liquid crystal composition which exhibits a birefringence Δn (λ) at a wavelength (λ) of a liquid crystal phase and which exhibits a nematic phase or a smectic phase and which has at least one kind of liquid crystal compound satisfying the following formula (1) Lt; / RTI &gt;

(1)? N (450 nm) /? N (550 nm) <1.

Among the optically anisotropic films, the molecules of the liquid crystal compound are fixed in the oblique alignment state. The inclined alignment state can be largely divided into a hybrid orientation in which the inclination angle (tilt angle) of the liquid crystalline molecules is different near the upper surface interface and the lower surface interface, and a nearly uniaxial tilt alignment in the vicinity of the upper surface interface and the lower surface interface. The optically anisotropic film of the invention may be formed by fixing a certain oblique orientation state. The hybrid alignment has a tilt angle difference of 5 占 or more in the vicinity of the upper interface and the lower interface. It is preferable that the tilt angle continuously changes from the upper surface interface to the lower surface interface. As a hybrid alignment mode, when an optically anisotropic film is formed on the surface of a substrate such as a polymer film or a glass plate, a tilt angle is increased toward the film surface farther from the film surface near the substrate, There is a form in which the tilt angle is reduced toward the film surface farther from the film surface on the side of the film surface.

In order to sufficiently exhibit the optical compensation ability, in the optically anisotropic film of the present invention, the average tilt angle of molecules of the liquid crystal compound is preferably 5 째 to 85 째 in absolute value, more preferably 15 째 to 55 째 , More preferably 20 [deg.] To 45 [deg.]. The average tilt angle can be obtained by applying a crystal rotation method. Or the hybrid alignment optically anisotropic film, directors of the liquid crystal molecules are at different angles at all positions in the thickness direction of the layer. Therefore, when the optically anisotropic film is viewed as a structure, there is no optical axis.

The optically anisotropic film can be produced by tilting the nematic liquid crystal so as to be in the range of the average tilt angle and fixing it in the aligned state. And may be made of any material and is not limited to a fixed aspect as long as the above conditions are satisfied. For example, it can be produced by aligning a low molecular weight liquid crystal in a liquid crystal state and then immobilizing it by photo-crosslinking or thermal crosslinking. It is also possible to produce the polymer liquid crystal by orienting the polymer liquid crystal in a liquid crystal state and cooling it to fix it.

Alternatively, a smectic liquid crystal may be immobilized. In the case of using a smectic liquid crystal, the Smectic liquid crystal is uniformly horizontally aligned, and then fixed by polymerization, photo-crosslinking, or thermal crosslinking to form an alignment transition in a hybrid orientation. This mechanism can be regarded as a result of focal conic transformation of the interval of the interval of the smectic layer due to polymerization shrinkage, which leads to a hybrid orientation by warping the smectic layer. Therefore, the control of the inclination angle can be performed by controlling the polymerization shrinkage rate and the polymerization progress speed. The Smectic liquid crystal can be more preferably used in the use requiring a comparatively large retardation of 100 nm or more because scattering polarization resolution of the optically anisotropic film is small due to alignment disorder. The smectic phase is not particularly limited, and SmA, SmB, SmC or a higher order phase may be used.

The thickness of the optically anisotropic film is preferably 0.1 to 20 탆, more preferably 0.2 to 15 탆, still more preferably 0.3 to 10 탆. The in-plane retardation (Re) (550 nm) of the optically anisotropic film at a wavelength of 550 nm is in a range of 10 nm to 250 nm, although the preferable range differs depending on the application.

[Liquid crystal compound used for production of optically anisotropic film]

The birefringence Δn (λ) at the wavelength (λ) of the liquid crystal phase is preferably at least 450 to 550 nm (preferably, in the entire visible light region), and the nematic phase and the smectic phase are produced in the production of the optically anisotropic film. And at least one liquid crystal compound having a property of increasing the birefringence as the wavelength becomes longer. Concretely, at least one kind of liquid crystal compound satisfying the following formula (1) is used.

DELTA n (450 nm) / DELTA n (550 nm) < 1

Further, in the case where the liquid crystal compound is in the same liquid crystal phase, the wavelength dependence of the birefringence is hardly dependent on temperature. To further clarify the present invention,? N (450 nm) measured at a temperature lower than the upper temperature of the phase transition temperature by 20 占 폚 It is assumed that? N (550 nm) satisfies the above formula (1). When the temperature range indicating the liquid crystal phase is 20 占 폚 or less, the value measured at a temperature lower than the upper limit temperature of the liquid crystal phase by 10 占 폚. When the temperature range representing the liquid crystal phase is 10 占 폚 or lower, When the measured value and the temperature range indicating the liquid crystal phase are 5 占 폚 or less, the value measured at a temperature lower than the upper limit temperature by 2 占 폚 is supposed to satisfy the above formula (1).

The preferable range of the wavelength dependency of? N of the liquid crystal compound differs depending on the use, but can not be determined uniquely. When the liquid crystal compound is used for viewing angle compensation of a reflective transmissive liquid crystal display device described later, (2) and (3).

0.60 <? N (450 nm) /? N (550 nm) <0.99

1.01 < DELTA n (650 nm) / DELTA n (550 nm) < 1.35

In the above equations (1), (2) and (3),? N (450),? N (550) and? N (650) represent? N at 450 nm, 550 nm and 650 nm, respectively. However, each measurement wavelength includes an error of +/- 10 nm.

As a method of measuring the n value of the liquid crystal, for example, a method of using a wedge-shaped liquid crystal cell as described in "Liquid Crystal Handbook" 2.4.13 (Maruzen Co., Ltd., 2000) can be mentioned. In this method,? N of each wavelength is obtained by using three kinds of band-pass filters of 450 nm, 550 nm and 650 nm. Further, in the case where the liquid crystal compound has a polymerizable group, the polymerization reaction may occur in the wedge-shaped liquid crystal cell, which makes measurement difficult. In such a case, it is preferable to measure by adding a polymerization inhibitor. In the state where the liquid crystal is uniformly oriented, Re is measured at each wavelength by measuring with a device capable of measuring retardation such as, for example, KOBRA (trade name, manufactured by Oji Measurement Instruments Co., Ltd.) By measuring the film thickness separately,? N can be obtained (from the equation of? N = Re / d (film thickness)).

Examples of the liquid crystal compound used in the production of the optically anisotropic film include a compound represented by the following general formula (I).

(3)

The compound of formula (I)

In the formulas, A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -NR- (R represents a hydrogen atom or a substituent), -S-, and -CO-. Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16 and forms a 5 or 6-membered ring together with the CC = CC or C = CC = C described in the formula . R ¹ , R ² and R ³ each independently represent a substituent. m is an integer of 0 to 4; L ¹ and L ² each independently represent a single bond or a divalent linking group. X represents a nonmetal atom of Groups 14 to 16 (provided that X may be bonded with a hydrogen atom or a substituent R ⁴ ). At least one of R, R ¹ , R ² , R ³ and R ⁴ has a polymerizable group.

Among the compounds represented by the above general formula (I), compounds represented by the following general formula (II) are preferable.

[Chemical Formula 4]

In general formula (II)

In the formulas, A ¹ , A ² , Z, R ¹ , R ² , R ³ , m, L ¹ and L ² are the same as those in formula (I). R ⁵ and R ⁶ each independently represent a substituent. At least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ has a polymerizable group.

In the general formula (I) or (II), L ¹ and L ² Is not particularly limited, but the following examples are preferable. Further, with respect to the bonding position, it is assumed that the bonding position of the 5- to 6-membered ring formed by Z and CC = CC or C = CC = C is on the left side of the linkage illustrated below.

[Chemical Formula 5]

More preferably -O-, -COO-, and -OCO-.

In the general formula (I) or (II), Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16, and CC = CC or C = CC = C to form a 5 or 6 atomic ring. The 5- to 6-membered ring formed by Z and CC = CC or C = CC = C is not particularly limited, but the following examples are preferable. Further, in the following examples, the dotted line indicates that it is bonded to L ¹ or L ² .

[Chemical Formula 6]

The ring formed by Z and C-C = C-C or C = C-C = C is preferably a six-membered ring. By making it a 6-atom ring, it becomes possible to orient the alignment in a higher degree of order. For the same reason, it is also preferable that the ring is an aromatic ring, more preferably an aromatic ring and a six-membered ring.

From these viewpoints and synthesis point of view, the ring formed by Z and C-C = C-C or C = C-C = C is preferably a thiophene ring, a benzene ring or a pyridine ring, and a benzene ring is most preferable.

In the general formula (I) or (II), R ¹ is a substituent and when a plurality of R ¹ is present, they may be the same or different or may form a ring. Examples of the substituent include the following.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, (Preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, an isopropyl group, a tert-butyl group, an n-octyl group and a 2-ethylhexyl group) Cyclohexyl group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms, such as hydrogen 2, 2] heptane-2-yl group, a bicyclo [2,2,2] octane-3-yl group), a monocyclic group

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as a vinyl group and an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, In other words, it is a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group Or a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. 2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), an alkynyl group A substituted or unsubstituted alkynyl group having from 1 to 30 carbon atoms, such as an ethynyl group or a propargyl group)

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a substituted or unsubstituted aromatic group having 5 or 6 atoms, Or a monovalent group in which one hydrogen atom has been removed from a non-aromatic heterocyclic compound, more preferably a 5- or 6-atom aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl group, 2 A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a thienyl group, a 2-pyrimidinyl group or a 2-benzothiazolyl group) (For example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy and 2-methoxyethoxy groups) An aryloxy group of a ring, for example, a phenoxy group, 2-methylphenyl Group, 4-tert- butylphenoxy group, a 3-nitro phenoxy group, 2-tetra-decanoyl-amino-phenoxy),

(Preferably a silyloxy group having 3 to 20 carbon atoms such as a trimethylsilyloxy group and a tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms (2-tetrahydropyranyloxy group), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heterocyclic oxy group, A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms such as a formyloxy group, an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxy A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy group, N, N-diethyl Carbamoyloxy group, morpholinocarbonyloxy group, N, N-di an n-octylcarbamoyloxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, a methoxycarb An alkoxycarbonyloxy group, an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryl group having 7 to 30 carbon atoms), an aryloxycarbonyloxy group An oxycarbonyloxy group such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group),

(Preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms such as an amino group, a methylamino group, a dimethylamino group, an anilino group, an N (Preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms (E.g., a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a formylamino group, an acetylamino group, a pivaloylamino group, a lauroylamino group or a benzoylamino group), an aminocarbonylamino group For example, carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, n (E.g., an octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenox A p-chlorophenoxycarbonylamino group, an m-octyloxyphenoxycarbonylamino group),

A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, an N-octylaminosulfonylamino group) An arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms such as a methylsulfonylamino group, a butylsulfonylamino group, A phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group), a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms (For example, a methylthio group, an ethylthio group, an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as a phenylthio group, a p- Claw (Preferably, a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-benzothiazolylthio group, 1-methoxyphenylthio group, Phenylthiazol-5-ylthio),

(Preferably a substituted or unsubstituted sulphamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethyl (Preferably having 1 to 20 carbon atoms), a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, an N-acetylsulfamoyl group, an N-benzoyl sulfamoyl group and an N- (N'-phenylcarbamoyl) sulfamoyl group) A substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group or a p-methylphenylsulfinyl group), alkyl or arylsulfo group (Preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p- Methylphenylsulfonyl group),

(Preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms such as an acetyl group and a pivaloylbenzoyl group), an aryloxycarbonyl group (Preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, or a p-tert-butylphenoxycarbonyl group) An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group , A substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di - octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group),

Aryl or heterocyclic azo group (preferably a substituted or unsubstituted aryl azo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms such as a phenyl azo group, a p-chlorophenyl azo group, a 5-ethyl (Preferably an N-succinimide group, an N-phthalimide group), a phosphino group (preferably having 2 to 6 carbon atoms) (Preferably a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms), a substituted or unsubstituted phosphino group having 1 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, (Preferably a phosphinyl group of 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxy phosphine group and a diethoxy phosphine group), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, For example, diphenylphosphinyloxy group, dioctyloxyphosphinyloxy (Preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group), a silyl group (preferably a silyl group having a carbon number of 3 A substituted or unsubstituted silyl group of 1 to 30 carbon atoms, for example, a trimethylsilyl group, a tert-butyldimethylsilyl group, a phenyldimethylsilyl group)

Of the above substituents, those having a hydrogen atom may be removed and substituted by the above-mentioned groups. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ¹ is preferably a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group or an amino group, An atom, an alkyl group, a cyano group or an alkoxy group.

When a plurality of R ^{1 s} exist to form a ring with each other, the ring is preferably a 5- to 8-membered ring, more preferably a 5-or 6-membered ring. Most preferably a 6-membered ring.

In the general formula (I) or (II), m represents a substitution number of R ¹ , and the number which can be taken by the structure of the ring formed by Z and CC = CC or C = CC = C is changed . m is at the minimum of 0 and Z is 2 carbon atoms and the ring formed by Z and CC = CC or C = CC = C is not aromatic. m is preferably 0 or 1, and more preferably 0. [

In the general formula (I) or (II), R ² and R ³ each independently represent a substituent. An example of R ¹ is mentioned as an example. R ² and R ³ are the longitudinal direction of the molecule in the compound represented by the general formula (I) or (II).

It is preferable that the compound represented by the general formula (I) or (II) exhibits liquid crystallinity. As described in "Chapter 3" Molecular Structure and Liquid Crystallinity ", a rigid portion called a core and a flexible portion called a side chain are required as factors for expressing liquid crystalline properties. Therefore, it is preferable that at least one rigid portion, that is, an annular portion exists as a substituent of R ² and R ³ . R ² and R ³ Is preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Preferably a phenyl group having a substituent or a cyclohexyl group having a substituent, more preferably a phenyl group having a substituent at the 4-position, or a cyclohexyl group having a substituent at the 4-position. More preferably a phenyl group having a benzoyloxy group at a 4-position at a 4-position, a phenyl group at a 4-position of a cyclohexyl group having a substituent at a 4-position, a cyclohexyl group having a phenyl group at a 4- , And a cyclohexyl group having a cyclohexyl group having a substituent at 4 position at 4 positions. More preferably, each of R ² and R ³ is a group represented by any one of the following formulas.

(7)

Wherein L ¹¹ is a single bond or a linking group, and R ¹¹ is a substituent. L ¹¹ is preferably a single bond or -O-, -COO- or -OCO-. Examples of the substituent represented by R ¹¹ are the same as the examples of the substituent represented by R ¹ . Among them, a substituted or unsubstituted alkylcarbonyloxy group having 1 to 10 carbon atoms (including cycloalkylcarbonyloxy), a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted or unsubstituted C6- A substituted or unsubstituted C1-C8 alkylcarbonyloxy group or a substituted or unsubstituted C1-C10 alkoxy group is more preferable. In the alkyl moiety in the alkylcarbonyloxy group or the alkoxy group, one of the non-adjacent carbon atoms may be substituted with an oxygen atom or a sulfur atom. The preferred examples of the alkyl moiety at the terminal of the polymerizable group include a group having a polymerizable group which will be described later, such as a group having (M-1) and (M-2) at the terminal, but the present invention is not limited thereto.

As the cyclohexyl group having a substituent at the 4-position, a stereoisomer of a cis structure or a trans isomer exists, but the present invention is not limited thereto, and a mixture of both may be used. Preferably a trans-cyclohexyl group.

In the general formula (I) or (II), R ⁵ and R ⁶ each independently represent a substituent. An example of R ¹ is mentioned as an example. Preferably, at least one of R &lt; ⁵ &gt; and R &lt; ⁶ &gt; is an electron-withdrawing substituent having a Hammett's substituent constant sigma _p value of more than 0 and preferably has an electron withdrawing substituent having a sigma _p value of 0 to 1.5 More preferable. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R ⁵ and R ⁶ may combine to form a ring.

As for the substituent constants σ _p and σ _m of Hammett, for example, see Inamoto Naoki, "Hammett Rule-Structure and Reactivity-" (Maruzen), edited by Nippon Kagaku Kogaku Synthesis and Reaction of Compounds ", page 2605 (Maruzen), Tadao Nakaya," Theory of Organic Chemistry ", page 217 (Tokyo Chemical Society)," Chemical Review ", vol. 91, pp. 165-195 Are described in detail in the literature.

In the general formula (I) or (II), A ¹ and A ² are each independently selected from the group consisting of -O-, -NR- (R is a hydrogen atom or a substituent), -S- and -CO- Lt; / RTI &gt; Preferably -O-, -NR- (R represents a substituent, examples of which include the examples of R ¹ above) or S-.

In the general formula (I), X represents a nonmetal atom of Groups 14 to 16. However, a hydrogen atom or a substituent may be bonded to X. X is the = O, = S, = NR 4, = C (R 5) R 6 is preferred. Here, R ⁴ , R ⁵ and R ⁶ each independently represent a substituent, and examples thereof include the above-mentioned R ¹ .

Preferable examples of R ⁵ and R ⁶ include a cyano group (CN), an acyl group (-COR: R represents a substituted or unsubstituted alkyl group or aryl group), a substituted or unsubstituted alkoxycarbonyl group or an aryloxycarbonyl group (C (C (= O) NR ¹¹ R ¹² : R ¹¹ and R ¹² each represent a hydrogen atom or a substituted or unsubstituted alkyl group or a substituted or unsubstituted carbamoyl group An alkyl group or an aryl group of a ring, which may be bonded to each other to form a ring). R, R ¹¹ and R a substituted or unsubstituted alkyl group ¹² represents the C ₁ ~ preferably a substituted or unsubstituted alkyl group of C _10, more preferably a substituted or unsubstituted alkyl group of C ₂ ~ C _8, and C ₂ More preferably a substituted or unsubstituted alkyl group having ₁ to ₆ carbon atoms. In addition, one of the non-adjacent carbon atoms in the alkyl group may be substituted with an oxygen atom or a sulfur atom. Examples of the substituted or unsubstituted aryl group represented by R, R ¹¹ and R ¹² include specific examples of the aryl group as an example of R ¹ . Examples of the substituent of the alkyl group and the aryl group are the same as the examples of the substituent represented by R ¹ . It is also preferable to have a polymerizable group described later as a substituent. An example of a ring formed by bonding R ¹¹ and R ¹² to each other includes a piperazine ring.

Among them, it is preferable that one of R ⁵ and R ⁶ is a cyano group and the other is a substituted or unsubstituted alkoxycarbonyl group.

The liquid crystal compound represented by the above general formula (I) or (II) has a polymerizable group. Thereby, it becomes possible to fix in a predetermined alignment state, and thereafter, it is possible to prevent a change in retardation due to heat or the like. The polymerizable group is preferably present at the molecular end. In the general formula (I) or (II), at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ has a polymerizable group. The number of polymerizable groups in one molecule is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3. It is more preferable that any of R ² , R ³ , R ⁵ and R ⁶ has a polymerizable group.

Preferable examples of the polymerizable group substituted by at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ include groups capable of addition polymerization reaction or condensation polymerization reaction.

As such a polymerizable group, a polymerizable ethylenic unsaturated group or a ring-opening polymerizable group is preferable. Examples of polymerizable groups are shown below.

[Chemical Formula 8]

It is particularly preferable that the polymerizable group is a functional group capable of an addition polymerization reaction. As such a polymerizable group, a polymerizable ethylenic unsaturated group or a ring-opening polymerizable group is preferable.

The polymerizable group is preferably a group represented by any one of the following general formulas P1, P2, P3 and P4.

[Chemical Formula 9]

In the formula, R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ each independently represent a hydrogen atom Or an alkyl group. n represents 0 or 1;

R ⁵¹¹ , R ⁵¹² and R ⁵¹³ of the polymerizable group (P1) Each independently represent a hydrogen atom or an alkyl group. The alkoxy group, alkoxycarbonyl group or alkoxycarbonyloxy residue in which the polymerizable group (P1) is substituted is an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptylene A substituted alkyleneoxy group containing an ether bond such as ethyleneoxyethoxy), an alkylenoxycarbonyloxy group (e.g., ethyleneoxy carbonyloxy, propyleneoxy carbonyloxy, butylene An alkyleneoxycarbonyloxy group such as benzyloxycarbonyloxy, pentylenecarbonyloxy, pentylenecyloxycarbonyloxy, hexylenecyloxycarbonyloxy or heptylenecyloxycarbonyloxy, or an alkyleneoxycarbonyloxy group such as ethyleneoxyethoxycarbonyloxy or the like A substituted alkyleneoxycarbonyloxy group), an alkyleneoxycarbonyl group (e.g., an ethyleneoxycarbonyl group, a propyleneoxycarbonyl group, a butyleneoxycarbonyl group, a pentylenoxy Viterbo group, a cyclohexylene oxycarbonyl group, heptyl oxy-ethylene optionally substituted alkyl of the alkyleneoxy group, or ethylene oxide, such as carbonyl group-containing an ether bond, such as ethoxycarbonyl group represents an alkyleneoxy group). The polymerizable group (P1) may be bonded directly to the aromatic ring.

n is an integer of 0 to 1, n is preferably 1, and when n is 1, the polymerizable group (P1) represents a substituted or unsubstituted vinyl ether group. R ⁵¹¹ and R ⁵¹³ each independently represent a hydrogen atom or an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, , R ⁵¹¹ is a methyl group, R ⁵¹³ is a hydrogen atom, or R ⁵¹¹ and R ⁵¹³ are both a hydrogen atom.

R ⁵¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, , Methoxyethoxyethyl, lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable), and hydrogen atoms and lower alkyl groups are preferable, and hydrogen atoms are more preferable. Therefore, as the polymerizable group (P1), an unsubstituted vinyloxy group, which is generally a functional group having a high polymerization activity, is preferably used.

The polymerizable group (P2) represents a substituted or unsubstituted oxyl group. R ⁵²¹ and R ⁵²² each independently represent a hydrogen atom or an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, , More preferably methyl), and R ⁵²¹ and R ⁵²² are both preferably hydrogen atoms.

R ⁵²³ represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, , Methoxyethoxyethyl, lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable), and hydrogen atoms or lower alkyl groups such as methyl, ethyl, n-propyl and the like are preferable.

The polymerizable group (P3) represents a substituted or unsubstituted acrylic group. The substituents R ⁵³¹ and R ⁵³³ each independently represent a hydrogen atom, an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, Ethyl, etc., more preferably methyl), R ⁵³¹ is methyl and R ⁵³³ is a hydrogen atom, or a combination of R ⁵³¹ and R ⁵³³ are all hydrogen atoms.

R ⁵³² represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, , Methoxyethoxyethyl, lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable), and hydrogen atoms are preferable. Therefore, as the polymerizable group (P3), a functional group having a high polymerization activity such as an unsubstituted acryloxy group, methacryloxy group, crotonyloxy and the like is preferably used.

The polymerizable group (P4) represents a substituted or unsubstituted oxetane group. R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ Is preferably a hydrogen atom or an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, And more preferably methyl), and it is preferable that R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ are both hydrogen atoms.

R ⁵⁴¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, , And methoxyethoxyethyl, and lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable), and hydrogen atoms or lower alkyl groups such as methyl, ethyl, n-propyl and the like are preferable.

Specific examples of the compound represented by the above general formula (I) or (II) are shown below, but the present invention is not limited at all by the following specific examples. The following compounds are indicated by the number in parentheses () as Exemplified Compound (X) unless otherwise specified.

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The synthesis of the compound represented by the above general formula (I) or (II) can be carried out by referring to a known method. For example, the exemplified compound (2) can be synthesized according to the following scheme.

[Chemical Formula 17]

Of the above schemes, the synthesis of the compound (2-1) to the compound (2-3) is carried out by referring to the method described in Journal of Chemical Crystallography (1997), 27 (9), p.515-526. can do.

Compound (2-6) is obtained from the compound (2-4) and the compound (2-5) by esterification with a conventional method using dicyclohexylcarbodiimide (DCC) as shown in the above scheme. A small amount of a polymerization inhibitor (Irganox 1010, trade name, manufactured by Ciba Specialty Chemicals) was added to N-methyl-2-pyrrolidone (NMP) suspension solution of the compound (2-3) Compound (2-7) is obtained. (2-9) obtained by the synthesis of an acid chloride in a method using thionyl chloride from the compound (2-8) by adding pyridine (Py) as a base to a tetrahydrofuran (THF) solution of the compound (2-7) ) Is added to obtain the exemplified compound (2).

[Method of forming optically anisotropic film]

The optically anisotropic film of the present invention can be produced by forming an orientation film on a solid phase such as a polymer film, a glass or a color filter if necessary, and applying a composition containing the compound represented by the above general formula (I) or (II) , And is formed by orientation and immobilization. The application of the liquid crystal composition can be carried out by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method) . It may also be formed by ejecting using an inkjet apparatus.

The &quot; immobilized &quot; state is the most typical and preferable mode in which the orientation of the liquid crystal compound contained in the optically anisotropic film is maintained, but is not limited thereto. Specifically, it is typically 0 deg. C to 50 deg. Under the harsh conditions, the optically anisotropic film has no fluidity in the temperature range of -30 ° C to 70 ° C and does not cause any change in the orientation form due to exterior or external force, and can stably maintain the fixed orientation form .

As a method for fixing the alignment state in the present invention, the liquid crystal composition is once heated to the liquid crystal phase formation temperature, and then cooled in a state in which the liquid crystal composition is maintained in the aligned state, And immobilized without causing any harm. Alternatively, the liquid crystal composition of the present invention to which the polymerization initiator is added may be heated to the liquid crystal phase formation temperature, and then polymerized and cooled to fix the alignment state of the liquid crystal phase. It is preferable to carry out the latter polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat, Polymerization by irradiation is preferred. Further, in the present invention, when the optically anisotropic film is finally formed, if the optical anisotropy is maintained, the liquid crystal compound does not need to be already liquid crystalline. For example, a low molecular weight liquid crystalline compound has a group which reacts with heat or light, and consequently, polymerization or crosslinking by reaction with heat, light or the like may result in high molecular weight and lose liquid crystallinity.

The liquid crystal temperature range of the liquid crystal composition is preferably in the range of 10 to 250 占 폚, more preferably in the range of 10 to 150 占 폚 in terms of suitability for production. If the temperature is lower than 10 占 폚, a cooling step or the like may be required to lower the temperature to the temperature range representing the liquid crystal phase. If the temperature is higher than 200 ° C, a high temperature is required in order to bring the isotropic liquid state to a higher temperature than the temperature range in which the liquid crystal phase is once displayed, which is also disadvantageous from waste of heat energy, deformation and deterioration of the substrate.

In the liquid crystal composition of the present invention, the liquid crystal compounds may be used singly or in combination. For example, a polymerizable liquid crystal compound and a non-polymerizable liquid crystal compound can be used in combination. It is also possible to use a combination of a low molecular weight liquid crystal compound and a high molecular weight liquid crystal compound. A plurality of liquid crystal compounds satisfying the above-mentioned formula (1) may be mixed. It is possible to expect an effect that the melting point is lowered by mixing and the liquid crystal temperature range is widened. As the liquid crystal compound satisfying the above-mentioned formula (1), for example, a liquid crystal compound described in JP-A-2005-289980 can be used as the liquid crystal compound other than the compound represented by the above general formula (I).

The optically anisotropic film is a liquid crystal composition prepared by mixing a liquid crystal compound satisfying the above formula (1) and a liquid crystal compound exhibiting a property that? N has a net dispersion wavelength dependency at a wavelength of 450 to 550 nm, that is, May be used. For example, a liquid crystal compound satisfying the following formula (4) may be used in combination.

(4)? N (450 nm) /? N (550 nm) > 1

By mixing a liquid crystal compound satisfying the above-mentioned formula (1) and a liquid crystal compound having a pure dispersion wavelength dependency, for example, satisfying the above formula (4), a liquid crystal composition exhibiting intermediate wavelength dependence It becomes possible to prepare it. Further, the mixing can increase the? N of the composition and form an optically anisotropic film having a desired retardation, which is advantageous in that the thickness can be reduced. The mixing ratio is not particularly limited, and the mixing ratio can be determined according to the intended use and desired optical characteristics.

The content of the liquid crystal compound represented by the general formula (I) or (II) in the liquid crystal composition (solid content excluding the solvent in the case of a liquid such as a coating liquid) used in the production of the optically anisotropic film of the present invention is 10 to 100 mass , More preferably from 40 to 100 mass%, still more preferably from 30 to 90 mass%, still more preferably from 50 to 90 mass%.

The liquid crystal composition may contain an optional additive in addition to the liquid crystal compound represented by the general formula (I) or (II). Examples of the additive include liquid crystal compounds other than the compounds represented by the above general formula (I) or (II), compounds for controlling the tilt angle of the liquid crystalline molecules described below, a nonuniformity inhibitor, an aggregation inhibitor, a polymerization initiator, .

[Compound for Controlling Tilt Angle of Liquid Crystalline Molecule]

The tilt angle of the optically anisotropic film on the side of the lower interface (that is, the substrate side interface when the optically anisotropic film is formed on the surface of the substrate such as a polymer film) and the tilt angle on the side of the upper interface (i.e., air interface) Can be controlled by selecting an air interface alignment agent to be added to the liquid crystal layer. Further, between the rubbing density of the alignment film and the tilt angle of the liquid crystal compound at the interface of the alignment film, there is a relation that the tilt angle becomes small when the rubbing density is made higher and the tilt angle becomes larger when the rubbing density is lowered. The tilt angle on the substrate side can be adjusted. Hereinafter, examples of the additive for decreasing and increasing the tilt angle at the air interface side and the additive for increasing the tilt angle at the alignment film side are given. The optically anisotropic film can be formed in such a manner that the optically anisotropic film is aligned in an approximately uniformly inclined state in the thickness direction or a hybrid orientation in which the tilt angle in the lower interface side is larger than the tilt angle in the air interface side, It is possible to form a hybrid orientation smaller than the tilt angle on the air interface side. Any form can be preferably used in the present invention.

In the composition for forming an optically anisotropic film, the following general formulas (X1) to (X3)

The tilt angle of molecules of the liquid crystalline compound in the air interface can be reduced or substantially horizontally aligned. In this case, by using a material having a high tilt in the alignment film, a hybrid alignment in which the tilt angle decreases from the substrate side to the image side of the optically anisotropic film is obtained. Since the degree of reduction of the tilt angle depends on the amount of addition, the target tilt angle can be obtained by adjusting the amount of addition. In this specification, the term &quot; horizontal alignment &quot; means that the long axis of the liquid crystal molecule is parallel to the film plane, and does not require strictly parallel alignment. In the present specification, the term &quot; horizontal alignment &quot; do.

Hereinafter, the following general formulas (X1) to (X3) will be described in order.

[Chemical Formula 18]

In general formula (X1)

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ³ represent a single bond or a divalent linking group. The substituent represented by each of R ¹ to R ³ is preferably a substituted or unsubstituted alkyl group (among these, an unsubstituted alkyl group or a fluorine-substituted alkyl group is more preferable), an aryl group (in particular, an aryl group having a fluorine- A substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. X ^1, X ² and X ³ with a divalent linking group representing each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic ^{residue, -CO-, -NR a - (R} a is a carbon atom number of from 1 to Is preferably a divalent linking group selected from the group consisting of -O-, -S-, -SO-, -SO ₂ -, and combinations thereof. The divalent linking group is preferably a divalent linking group selected from the group consisting of an alkylene group, a phenylene group, -CO-, -NR ^a -, -O-, -S- and -SO ₂ - More preferably a divalent linking group formed by combining two or more divalent linking groups. The number of carbon atoms of the alkylene group is preferably 1 to 12. The number of carbon atoms of the alkenylene group is preferably from 2 to 12. The number of carbon atoms of the divalent aromatic group is preferably 6 to 10.

[Chemical Formula 19]

In general formula (X2)

In the formulas, R represents a substituent and m represents an integer of 0 to 5. When m represents an integer of 2 or more, a plurality of Rs may be the same or different. The preferable substituents for R are the same as those listed as preferable ranges of the substituents represented by R ¹ , R ² , and R ³ . m is preferably an integer of 1 to 3, and particularly preferably 2 or 3.

[Chemical Formula 20]

In general formula (X3)

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituent represented by each of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably a substituent represented by R ¹ , R ² and R ³ in the formula (XI) will be. As the horizontal alignment agent used in the present invention, the compounds described in Japanese Patent Application No. 2003-331269 (Japanese Patent Application Laid-Open No. 2005-099258) can be used, and the synthesis method of these compounds is also described in the specification.

The amount of the compound represented by any one of formulas (X1) to (X3) is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and more preferably 0.02 to 1% by mass relative to the mass of the liquid crystalline compound Particularly preferred. The compounds represented by the above general formulas (X1) to (X3) may be used alone or in combination of two or more.

By containing, for example, a compound having an acidic group such as -COOH or -SO ₃ H group as a functional group in the molecule as represented by the following AE-1 to A-4 in the composition for forming an optically anisotropic film, The tilt angle of the molecules of the liquid crystal compound can be increased or substantially vertically aligned. In this case, by using a low tilt angle in the orientation film, a hybrid orientation in which the tilt angle increases from the substrate side of the retardation layer toward the air interface side is obtained.

The amount of the compound to be added is preferably from 0.01 to 20% by mass, more preferably from 0.01 to 10% by mass, based on the mass of the liquid crystalline compound, depending on the target tilt angle since the tilt angle can be increased as the addition amount is increased , And particularly preferably from 0.02 to 1% by mass.

[Chemical Formula 21]

The composition for forming an optically anisotropic film contains at least one kind of compound having an ionic low molecular weight compound, especially a cationic group larger than an anionic group, so that the tilt angle of molecules of the liquid crystalline compound is increased or substantially It can be vertically aligned. Specific examples of the compound include compounds represented by the following PE-1 to 6, for example. Since the degree of increase of the tilt angle is dependent on the addition amount, the target tilt angle can be obtained by adjusting the amount of addition.

The amount of the compound to be added is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass, based on the mass of the liquid crystalline compound.

[Chemical Formula 22]

(Non-uniformity inhibitor)

In addition, when the desired an additive is used in forming the optically anisotropic film, occurrence of non-uniformity of optical properties in the optically anisotropic film can be reduced. With this additive, the surface tension of the coating liquid can be lowered and the coating stability can be enhanced. The surface tension of the coating liquid at this time is preferably 25 to 20 dyn / cm, more preferably 23 to 21 dyn / cm. The amount of the additive to be used is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.5% by mass, based on the total mass of the liquid crystal composition (solid content in the case of the coating liquid). The compound of this additive is not particularly limited and may be a low molecular compound or a high molecular compound. As the fluorine-containing surfactants and silicon compounds, the following fluorine-containing compounds may be preferably used. As a result of using these additives, it contributes to improvement in non-uniformity of display characteristics when used in a liquid crystal display device.

(23)

(Aggregation inhibitor)

An anti-aggregation agent may be added to the liquid crystal composition for forming an optically anisotropic film to prevent lumps when applying the liquid crystal composition. As the aggregation inhibitor, a polymer is generally preferably used. The polymer to be used is not particularly limited so long as it does not significantly change the inclination angle or orientation of the liquid crystal compound. Examples of polymers include those described in JP-A-8-95030, and specific examples of polymers that are particularly preferable include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropylcellulose and cellulose acetate butyrate.

The content of the polymer used for preventing aggregation so as not to impede the orientation of the liquid crystal is generally in the range of preferably 0.1 to 10 mass%, more preferably 0.1 to 8 mass%, with respect to the liquid crystal compound , And more preferably from 0.1 to 5 mass%.

(Polymerization initiator)

The liquid crystal composition for forming an optically anisotropic film is preferably a curable composition, and for this purpose, it preferably contains a polymerization initiator. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat, Polymerization by irradiation is preferred.

-카르보닐 화합물 (미국 특허 제2367661호, 동 제2367670호의 각 명세서 기재), 아실로인에테르 (미국 특허 제2448828호 명세서 기재),

-탄화수소 치환 방향족 아실로인 화합물 (미국 특허 제2722512호 명세서 기재), 다핵 퀴논 화합물 (미국 특허 제3046127호, 동 제2951758호의 각 명세서 기재), 트리아릴이미다졸다이머와 p-아미노페닐케톤과의 조합 (미국 특허 제3549367호 명세서 기재), 아크리딘 및 페나진 화합물 (일본 공개특허공보 소60-105667호, 미국 특허 제4239850호 명세서 기재) 및 옥사디아졸 화합물 (미국 특허 제4212970호 명세서 기재) 등을 들 수 있다. As examples of the photopolymerization initiator,

-Carbonyl compounds (described in U.S. Patent Nos. 2367661 and 2367670), acyloin ethers (described in U.S. Patent No. 2448828)

-Hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent No. 2722512), polynuclear quinone compounds (described in U.S. Patent Nos. 3046127 and 2951758), triarylimidazodime and p-aminophenyl ketone (Described in U.S. Patent No. 3549367), acridine and phenazine compounds (Japanese Patent Application Laid-open No. 60-105667, U.S. Patent No. 4239850), and oxadiazole compounds (U.S. Patent No. 4212970 ) And the like.

The amount of the photopolymerization initiator to be used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the liquid crystal composition (solid content in the case of the coating liquid). It is preferable to use ultraviolet light for light irradiation for polymerization of the liquid crystal compound. The irradiation energy is preferably 10 mJ / cm 2 to 50 J / cm 2, more preferably 50 mJ / cm 2 to 800 mJ / cm 2. In order to promote the photopolymerization reaction, light irradiation may be carried out under heating conditions. When the oxygen concentration in the atmosphere does not reach the desired degree of polymerization in the air in order to participate in the degree of polymerization, it is preferable to lower the oxygen concentration by a method such as nitrogen substitution. The preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.

The reaction rate of the polymerization is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more from the viewpoints of maintaining the mechanical strength of the optically anisotropic film or inhibiting the unreacted materials from flowing out to the liquid crystal layer or the like. In order to improve the polymerization reaction rate, a method of increasing the irradiation amount of ultraviolet rays to be irradiated or a polymerization under a nitrogen atmosphere or heating conditions is effective. Alternatively, after the polymerization, the polymerization may be carried out at a temperature higher than the polymerization temperature to further promote the reaction by a thermal polymerization reaction, or a method of irradiating ultraviolet rays again may be used. The measurement of the polymerization reaction rate can be carried out by comparing the absorption intensity of the infrared vibration spectrum of the polymerization reactive bonding group before and after the polymerization.

(Polymerizable monomer)

The liquid crystal composition may contain a polymerizable monomer. The polymerizable monomer to be used together with the liquid crystal compound is not particularly limited as long as it has compatibility with the liquid crystal compound and does not significantly change the tilt angle of the liquid crystal compound or inhibit orientation. Of these, compounds having a polymerizable ethylenic unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group and a methacryloyl group are preferably used.

The content of the polymerizable monomer in the liquid crystal compound is generally in the range of 0.5 to 50 mass%, preferably in the range of 1 to 30 mass%. When a monomer having two or more reactive functional groups is used, for example, when an optically anisotropic film is formed on the surface of the alignment film, an effect of increasing the adhesion between the alignment film and the optically anisotropic film can be expected.

(Made in chiral)

The liquid crystal composition for forming the optically anisotropic film may contain at least one kind of chiral agent. When a liquid crystal composition containing a chiral agent is used, it is possible to exhibit a twist angle orientation or a twisted hybrid alignment structure. The chiral agent used in the present invention may be a chiral agent known in the art (see, for example, Japanese Laid-Open Patent Application No. 142 Pages, 1989) can be used.

The chiral agent generally contains an asymmetric carbon atom, and a condensed sub-title compound or a planar sub-title compound which does not contain an asymmetric carbon atom can also be used as a chiral agent. Examples of the builder subcomponent or the planar subcomponent include binaphthyl, heliin, paracyclophane, and derivatives thereof. The chiral agent may have liquid crystallinity, and the liquid crystal compound of the present invention may also serve as a chiral agent.

The amount of the chiral agent to be used is preferably 0.001 to 10 mol% of the amount of the liquid crystal compound. The amount of the chiral agent to be used is preferred because a smaller amount does not affect liquid crystallinity. Therefore, it is preferable that the chiral agent has a strong biting force. As such a biting force stronger chiral agent, for example, a chiral agent described in JP-A-2003-287623 can be used.

(Coating agent)

The liquid crystal composition may be prepared as a coating liquid. As the solvent used for preparing the coating liquid, an organic solvent is preferably used. Examples of the organic solvent include amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, heterocyclic compounds such as pyridine, hydrocarbons such as toluene and hexane, (For example, chloroform, dichloromethane), esters (e.g. methyl acetate, butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (e.g., tetrahydrofuran, 2-dimethoxyethane). Alkyl halides, esters and ketones are preferred. Two or more kinds of organic solvents may be used in combination.

[Orientation Layer]

As described above, an orientation layer may be used for forming the optically anisotropic film. The alignment layer functions to define the alignment direction of the liquid crystalline compound formed thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic film. Preferable examples of the alignment layer include a method of irradiating polarized light or natural light with a layer obtained by rubbing an organic compound (preferably a polymer), a four-way vapor deposition layer of an inorganic compound, or a compound capable of optical isomerization, (LB film) such as omega -tricoic acid, dioctadecylmethylammonium chloride and methyl stearate, or a layer formed by applying a total electric field or a magnetic field to a dielectric layer .

It is preferable to use a polymer for the formation of the orientation layer. The kind of polymer that can be used can be determined according to the orientation of the liquid crystalline compound (in particular, the average inclination angle). For example, in order to orient the liquid crystalline compound horizontally, a polymer (a polymer for general orientation) that does not lower the surface energy of the orientation layer is used. Regarding the specific types of polymers, there are various references to liquid crystal cells or optical compensation sheets. For example, there may be mentioned polymers such as polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, poly (N-methylol acrylamide), styrene / vinyl toluene copolymer, Polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, Silane coupling agents and the like. Examples of preferred polymers include alkyl-modified polyvinyl alcohol polyvinyl alcohols or modified polyvinyl alcohols having polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol and alkyl groups (preferably 6 or more carbon atoms) Or copolymers thereof with polyacrylic acid esters, polyvinylpyrrolidone, cellulose or modified cellulose are preferably used. The material for the alignment layer may have a functional group capable of reacting with the reactive group of the liquid crystalline compound. The reactive group may be introduced as a substituent of a cyclic group or by introducing a repeating unit having a reactive group into a side chain. It is more preferable to use an orientation layer which forms a chemical bond with the liquid crystalline compound at the interface. As such an orientation layer, it is described in Japanese Patent Application Laid-Open No. 9-152509, and an acid chloride or a current M0I ) Manufactured by Nippon Polyurethane Industry Co., Ltd.) is particularly preferable. The thickness of the orientation layer is preferably 0.01 to 5 탆, more preferably 0.05 to 2 탆.

In addition, a polyimide film (preferably a fluorine atom-containing polyimide) widely used as an alignment layer of an LCD is also preferable as an organic alignment layer. This is achieved by applying a polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Industries, Ltd.) to the support surface and firing at 100 to 300 ° C for 0.5 to 1 hour , And rubbing. The rubbing treatment may be a widely employed treatment method as a liquid crystal alignment treatment process of an LCD. That is, a method of obtaining the orientation by rubbing the surface of the orientation layer in a predetermined direction using a paper, a gauze, a felt, a rubber, nylon, or a polyester fiber can be used. Generally, this is carried out by rubbing the fabric several times by using a fabric which has an average fiber length and a uniform thickness.

Further, the inorganic vapor-deposited film all over the deposition material, there may be mentioned the SiO as a representative, and such as TiO _2, ZnO _2, such as a metal oxide, fluoride or MgF _2, and metals such as Au, Al. The metal oxide can be used as a four-sided vapor deposition material if it has a high dielectric constant, but is not limited thereto. The inorganic four-sided vapor deposition film can be formed using a vapor deposition apparatus. The inorganic sidewall vapor-deposited film can be formed by depositing the film (support) while fixing it, or continuously depositing the film by moving the long film.

As a compound used in a method of irradiating a polarized light or tilting natural light with a photoisomerizable compound, azo-based liquid crystalline compound, polymer or cinnamoyl-based compound is preferable because of high sensitivity to light. And may be increased or decreased by adding a photosensitizer or the like as necessary. Any of them can be preferably used as long as it functions as an orientation film by anisotropy generated on the film surface by isomerization or dimerization by light. Particularly, in the case where the barrier rib is formed on a color filter or a color filter having a large irregularity or a matrix shape in which a portion not subjected to rubbing treatment is generated, the use of the alignment film by this light is more preferable.

[Support]

The optically anisotropic film of the present invention may be formed on a support. When it is used in a liquid crystal display device, it can be formed directly on a glass substrate of a liquid crystal cell, a color filter in a cell, or an overcoat (OC) layer or via an orientation layer. On the other hand, after being formed on a support such as a transparent polymer film, it may be bonded to another member in the liquid crystal display device together with the support. Alternatively, after the optically anisotropic film is formed on the support, only the optically anisotropic film may be transferred to the surface of the other member in the liquid crystal display. As a laminate of the optically anisotropic film and the support, when used in a liquid crystal display device, the support preferably has a light transmittance, specifically a light transmittance of 80% or more. When used as the laminate, a support made of a polymer film or the like may be used as a protective film of the polarizing plate. When it is also used as a protective film of a polarizing film, the support is preferably a polymer film. Specific examples of the polymer include films of cellulose esters (e.g., cellulose diacetate, cellulose triacetate), norbornene polymers, and poly (meth) acrylate esters, and many commercially available polymers can be used have. Of these, cellulose esters are preferable from the viewpoint of optical performance, and a lower fatty acid ester of cellulose is more preferable. The lower fatty acid is preferably a fatty acid having 6 or less carbon atoms and the number of carbon atoms is 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose triacetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate or cellulose acetate butyrate may be used. It is also possible to use a conventionally known polymer such as polycarbonate or polysulfone, which is likely to exhibit birefringence, and whose expression is reduced by modifying a molecule described in WO 00/26705.

The support may be optically isotropic or may have anisotropy. A retardation layer having an optical compensation function such as a second optically anisotropic layer described later may be used as the support. The thickness of the polymer film used as a support is usually in the range of 5 to 500 μm, preferably in the range of 20 to 250 μm, more preferably in the range of 30 to 180 μm, and more preferably in the range of 30 to 110 μm Particularly preferred.

[First Aspect of Liquid Crystal Display Device of the Present Invention]

A first aspect of the liquid crystal display device of the present invention will be described with reference to the drawings. 1 is a schematic cross-sectional view of an example of a liquid crystal display device of the present invention. The reflective transmission type liquid crystal display device shown in Fig. 1 has a multi-gap liquid crystal cell, and a narrow gap portion is used as a reflective display portion and a wide gap portion is used as a transmissive display portion. The cell gap of the reflective display portion is adjusted to be approximately twice as large as that of the transmissive display portion.

The liquid crystal display device of Fig. 1 includes, in order from the observer side, a linear polarizer plate 1, a phase difference film 2, a substrate 3, a transmission color filter 4, a reflection color filter 5, A liquid crystal layer 8 having a thickness different from that of the transmissive portion and the reflective portion, a reflective plate 9 made of aluminum or the like, a substrate 10, a second optically anisotropic layer 13, A first optically anisotropic layer 14 made of an optically anisotropic film, and a backlight-side polarizing plate 12. A backlight unit including a light source, a light guide plate, a prism sheet, a diffuser plate, and a reflector disposed on the back surface of the light guide plate is disposed below the backlight side polarizing plate 12. If necessary, a polarizing plate or a cholesteric liquid crystal film (for example, a birefringent layer and an isotropic refractive index layer laminated on the optical thickness of? / 4) may be interposed between the backlight side polarizing plate 12 and the backlight And a polarizing reflection plate made of a? / 4 phase difference plate may be formed.

First, the reflective display section will be described. The light from the outside is converted into a polarization state close to circularly polarized light by the viewer side polarizing plate 1 and the retardation film 2 and then passes through the liquid crystal layer 8 and is reflected by the reflecting plate 9 serving also as an electrode And then passes again through the liquid crystal layer 8. In this process, the reflected circularly polarized state changes according to the voltage applied to the liquid crystal, so that the intensity of light passing through the viewer's side polarizing plate 1 can be modulated. For example, the in-plane retardation (Re) of the liquid crystal layer 8 is set to 50 nm or less in black display and 100 nm or more in white display. When the in-plane retardation Re of the liquid crystal layer 8 is 50 nm or less, the sense of the circularly polarized light is reversed in the reflection plate 9, so that light can not pass through the viewer-side polarizer 1 and becomes black. On the other hand, when the Re of the liquid crystal layer 8 is 100 nm or more, the circularly polarized light of the light passing through the liquid crystal layer 8 becomes closer to the incident light, so that the circularly polarized light is converted into linearly polarized light by the retardation film 2, And a bright display is obtained.

It is possible to adjust the retardation by supplying a voltage to the liquid crystal layer 8 as the tilt angle of the liquid crystal in the liquid crystal layer 8 becomes larger in black display than in white display.

On the other hand, in the transmissive display portion, the light incident from the backlight is converted into linearly polarized light by passing through the backlight side polarizing plate 12, passes through the first optically anisotropic layer 14 and the second optically anisotropic layer 13, . The circularly polarized light passes through the substrate 10 and enters the liquid crystal layer 8. The light incident on the liquid crystal layer 8 is changed in polarized state by the voltage applied to the liquid crystal layer to change the polarization state again by the retardation film 2 after passing through the transmissive color filter 4 And is absorbed or transmitted by the viewer side linearly polarizing plate 1 according to the polarization state thereof, and reaches the observer side. For example, as described above, when the in-plane retardation (Re) of the liquid crystal layer 8 is largely doubled in white display compared to black display, the polarization state of incident light is not impaired in black display Side polarizer 1, and when white display is performed, the circularly polarized light having passed through the liquid crystal layer 8 is reversed and passes through the viewer-side polarizer 1.

The retardation Re in the plane of the first optically-anisotropic layer 14 is preferably 80 nm to 160 nm, more preferably 100 nm to 150 nm at a wavelength of 550 nm, more preferably 100 nm to 150 nm, And even more preferably from nm to 140 nm.

The first optically anisotropic layer 14 is made of the optically anisotropic film of the present invention. That is, since? N is an optically anisotropic layer formed by obliquely aligning and fixing a liquid crystal compound exhibiting reverse dispersion wavelength dependence, Re of the first optically anisotropic layer 14 also exhibits reverse dispersion wavelength dependence. Since the color filters of the respective colors pass light having a wavelength distribution with a full width at half maximum of 100 nm to 150 nm, when Re uses an optically anisotropic layer having a pure dispersion wavelength dependency instead of the first optically anisotropic layer 14, The color compensation can not be achieved. By using the optically anisotropic film of the present invention exhibiting the reverse dispersion wavelength dependency as the first optically anisotropic layer 14, almost complete color compensation becomes possible. It is preferable that the phase angle difference due to the first optically anisotropic layer 14 corresponding to the central wavelength of each color of the color filter is substantially the same value regardless of the color.

The first optically-anisotropic layer 14 can be formed by adhering the liquid crystal compound described above and the one formed by the above-described production method to a liquid crystal display device together with a support via a direct adhesive or an adhesive, 14) can be transferred to a substrate of a liquid crystal display device or a phase difference plate formed on a substrate or the like. The support on which the optically anisotropic layer 14 is formed may be used as a protective film of a polarizing plate and adhered to a liquid crystal display device. Or may be formed directly on a substrate of a liquid crystal display device by coating and fixing using an inkjet method described later.

The second optically-anisotropic layer 13 has an effect of compensating birefringence of liquid crystal in black display of the liquid crystal layer 8, and this use has the effect of enlarging the contrast viewing angle. The retardation (Rth) in the thickness direction at a wavelength of 550 nm is 40 nm to 150 nm and the in-plane retardation (Re) at a wavelength of 550 nm is 0 nm- 20 nm. It is preferable that the retardation (Rth) in the thickness direction of the second optically-anisotropic layer at 450 nm is dispersed at a wavelength in the visible range. Specifically, it is more preferable that Rth (450 nm) and Rth (550 nm) satisfy the following formula (5) from the viewpoint of compensation of the liquid crystal layer, and more preferably satisfy the following formula .

(5) Rth (450 nm) / Rth (550 nm) > 1

Rth (450 nm) / Rth (550 nm) > 1.2 >

The second optically-anisotropic layer 13 is not limited to a material as long as it has the optical properties described above. For example, the second optically-anisotropic layer 13 may be a film obtained by biaxially stretching a polymer film such as polycarbonate or norbornene, A film which is horizontally aligned and fixed can be used. Alternatively, a polymer film such as cellulose acylate may be mixed with a compound that expresses the optical characteristics. In addition, by using the second optically anisotropic layer 13 as a support and forming the first optically anisotropic layer 14 thereon, the number of manufacturing steps can be reduced.

1 shows an example in which the first optically-anisotropic layer 14 is disposed between the backlight polarizing plate 12 and the substrate 10, it may be disposed between the substrate 3 and the viewer-side polarizing plate 1 , Or may be disposed at both positions. In this case, there is an effect of reducing the number of layers of the retardation layer to be used. 1 shows a configuration in which the second optically anisotropic layer 13 is disposed between the liquid crystal layer 8 and the first optically anisotropic layer 14, that is, the liquid crystal layer 8, the second optically anisotropic layer 13 and the first optically-anisotropic layer 14, the second optically-anisotropic layer 13 is arranged in a position sandwiching the liquid-crystal layer 8 between the first optically-anisotropic layer 14 and the first optically-anisotropic layer 14 The first optically anisotropic layer 14, the liquid crystal layer 8, and the second optically-anisotropic layer 13 are arranged in this order from the viewer side, that is, the second optically anisotropic layer 13, the liquid crystal layer 8, And the second optically anisotropic layer 13 may be arranged in this order.

[Second aspect of the liquid crystal display device of the present invention]

2 is a schematic schematic diagram of an example of the second aspect of the liquid crystal display device of the present invention. In the liquid crystal display device of this embodiment, similarly to the first embodiment shown in Fig. 1, a multi-gap liquid crystal cell is provided, and a narrow gap portion is used as a reflective display portion and a wide gap portion is used as a transmissive display portion. 1 is that the first optically anisotropic layer is formed between the pair of substrates 3 and the substrate 10. [ The second aspect is a so-called in-cell type liquid crystal display device. In the example shown in Fig. 2, the second optically-anisotropic layer 13 is not disposed. In this embodiment, however, it may be disposed between the first optically anisotropic layer and the liquid-crystal layer as necessary.

Modulation of light from the outside in the reflective display section is the same as that in Fig. 1, and a description thereof will be omitted.

Modulation of the light incident from the backlight is also the same. In this embodiment, the utilization efficiency of light can be further improved. Specifically, when the incident light from the backlight passes through the backlight side polarizing plate 12 and the substrate 10, part of the light is reflected as linearly polarized light on the back surface of the reflecting plate 9 formed on the reflective display portion, 12, and is returned to the backlight side and reused. In the conventional reflective transmissive liquid crystal display device (for example, the liquid crystal display device disclosed in Patent Documents 1 and 2), since the retardation film is disposed between the reflective plate and the backlight side polarizing plate, the polarization state is changed by 180 degrees, In this embodiment, since the light is reused, the light utilization efficiency can be improved.

Also in this embodiment, the first optically anisotropic layer 14 is made of the optically anisotropic film of the present invention. That is, since Re is an optically anisotropic layer formed by obliquely aligning and fixing a liquid crystal compound exhibiting reverse dispersion wavelength dependence, Re of the first optically anisotropic layer 14 also exhibits a reverse dispersion wavelength dependency. As a result, as described above, the color filter of each color can perform almost complete color compensation even when light having a wavelength distribution of a full width at half maximum of 100 nm to 150 nm is passed.

In the second embodiment, since the first optically anisotropic layer 14 is disposed corresponding to the pattern of each color of the color filter 4, the wavelength dependency of Re of the first optically anisotropic layer 14 is not in the optimum range If adjustment is necessary, for example, the thickness of the first optically anisotropic layer 14 may be made different from each other, and the value of Re may be adjusted to the optimum range for each wavelength of each color. Since the first optically-anisotropic layer 14 is made of the optically anisotropic film of the present invention, the wavelength dependence of Re is adjusted to some extent by the liquid crystal compound as the raw material, so that the difference in thickness between the color filters can be made small So that the planarization process of the step by the difference in the thickness becomes easy.

In the second embodiment, the first optically anisotropic layer 14 is formed only in the transmissive display portion of the liquid crystal display device. By this formation, since two conventionally disposed retardation plates can be omitted between the polarizing plate on the backlight side and the substrate, not only the cost reduction can be achieved but also the light reflected by the reflecting plate is not absorbed by the polarizing plate It is returned to the backlight side and reused, so that the luminance of the transmissive display can be improved. 2, the first optically-anisotropic layer 14 is formed on the phosphor-side surface of the backlight-side substrate 10, but may be formed on the phosphor-side surface of the visual-side polarization plate 3. In the example of Fig. 2, the position of the first optically-anisotropic layer 14 is preferably between the substrate 10 and the transparent electrode (not shown). The black matrix 6 and the like which are between the substrate 3 and the color filter 4 or between the color filter 4 and the transparent electrode (not shown) are formed on the phosphorus side of the substrate 3 on the viewer side Of the partition wall.

In the second embodiment, the first optically-anisotropic layer 14 is formed by ejecting and drying a fluid containing a liquid crystalline compound satisfying the above-described formula (1) from a jet head to a transmissive area, And then exposing it to light. According to this method, it can be formed with high accuracy at a position corresponding to the position of the color filter or the transmissive portion reflection portion. Of course, this method can also be used for the formation of the first optically-anisotropic layer 14 in the first aspect. In this case, there is an effect that the loss of the liquid coating liquid can be reduced as compared with other forming methods.

A method of forming the first optically anisotropic layer by using the ink jet method will be described in detail.

First, on a glass substrate, a substrate to which a black matrix having a surface treated with a gas containing F atoms (CF ₄ or the like) by plasma treatment or the like is attached is prepared, and a fine region divided by a black matrix , A solution containing a liquid crystalline compound, and the like are ejected by using an inkjet apparatus to form a layer made of the fluid in the fine region. The fluid contains at least one liquid crystal compound satisfying the above-mentioned formula (1), and is prepared so as to form a liquid crystal phase after drying. A liquid dispersion in which a part or all of a material such as a liquid crystalline compound is dispersed may be used, and it is preferably a solution. After the completion of the discharge of the solution, the solution is dried to form a liquid crystal phase, and then exposed to form a first optically anisotropic layer. In order to form a liquid crystal phase, it may be heated as desired, and in this case, a heating apparatus may be used.

In the case of forming the first optically anisotropic layer on the phosphor-side surface of the viewing side substrate (the substrate 3 in FIG. 2), on the optically anisotropic layer thus formed, the second ink The color filter layer of the transmissive portion may be formed by performing ejection, drying it, and exposing it as desired. The color filter layer of the reflective portion can also be formed by using the ink jet method. Thereafter, a planarization layer (the overcoat layer 7 in Fig. 2) may be formed on the color filter layer as necessary.

The first optically-anisotropic layer may be formed on the color filter layer (in FIG. 2, the color filter layer 4) of the transmissive portion. In this case, a color filter layer is formed by an ink jet method or the like, The first optically anisotropic layer can be formed.

(For example, 20 to 120 占 폚) when the viscosity of the fluid for forming the optically anisotropic layer is high, it is preferable that the viscosity of the liquid for forming the optically- , It is preferable from the viewpoint of injection stability that the ink viscosity is lowered. Since the viscosity fluctuation of ink or the like greatly affects the droplet size and droplet ejection speed as it is and causes deterioration of image quality, it is preferable to keep the temperature of the ink or the like as constant as possible.

The same applies to the case where the transmissive portion color filter layer and the reflective portion color filter layer (in Fig. 1, the color filter layers 4 and 5) are formed by inkjet.

The ink jet head (hereinafter, simply referred to as a head) used in the above method is not particularly limited, and various known ink jet heads can be used. Contineus type, dot on demand type can be used. Among dot-on-demand types, a type having a movable valve as described in JP-A-9-323420 is preferable for discharging in a thermal head. In the piezo head, for example, a head described in European Patent No. A277,703 or European Patent No. A278,590 can be used. The head preferably has a temperature control function to control the temperature of the composition. It is preferable to control the composition temperature so that the injection temperature is set to 5 to 25 mPa · s and the variation range of the viscosity is within ± 5%. It is preferable to operate at a drive frequency of 1 to 500 kHz.

Prior to the formation of the first optically anisotropic layer, a material such as polyvinyl alcohol, polyamic acid or soluble polyimide to be the above-mentioned alignment film is applied and dried, and if necessary, this surface is subjected to alignment treatment such as rubbing, Layer may be formed. Thereafter, the fluid may be discharged onto the rubbing treatment surface to form the first optically anisotropic layer. Further, a photo alignment film capable of imparting uniaxial alignment property by irradiation with polarized ultraviolet light or inclined irradiation with ultraviolet light can be preferably used. The orientation layer may be formed using an ink-jet method in the same manner as the retardation layer, or may be formed by another method.

The method of forming the first optically-anisotropic layer or the color filter layer in the first or second aspect of the second aspect is not limited to the ink-jet method. For example, a printing method or the like other than the ink- It is of course possible to form it by using.

[Orientation Arrangement of First Optically Anisotropic Layer]

In a preferred embodiment of the liquid crystal display of the present invention, the average direction of the axis in which the director of the liquid crystal molecules in the liquid crystal cell in the black display is projected on the layer parallel plane and the director of the oriented liquid crystal molecule in the first optically- And one direction is substantially parallel. Herein, &quot; substantially parallel &quot; in the present invention means that the angle difference between the two directions is from -10 degrees to less than 10 degrees, preferably from -5 degrees to less than 5 degrees, more preferably from -3 degrees to 3 degrees It says. The director of the liquid crystal molecules in the liquid crystal cell can be adjusted in a desired direction by the rubbing direction of the alignment film formed on the opposing face of the substrate. It is also preferable that the average oblique direction of the liquid crystal molecules in the first optically-anisotropic layer is inclined at an angle of 180 degrees with respect to the oblique direction of the liquid crystal molecules in the liquid crystal cell in the black display. The combination of these arrangements makes it possible to reduce the retardation dependency in the oblique direction in the black display and to enlarge the contrast viewing angle.

[Board]

The liquid crystal cell substrate used in the liquid crystal display device of the present invention is not particularly limited, and a substrate made of various materials conventionally used as a substrate of a liquid crystal cell can be used. For example, a metal support, a metal support, glass, ceramics, a synthetic resin film, or the like can be used. Particularly preferred are glass and synthetic resin films having transparency and excellent dimensional stability.

[Color filter layer]

The color filter is usually composed of color filter portions of R, G, and B and a black matrix that shields light. In the reflective transmission type, light having a lower absorption density than the color filter formed in the transmissive portion is used because the light passes through the color filter twice at the reflective portion. Alternatively, a means may be used in which a transparent resist layer is formed on a portion of the reflective portion where the color filter is to be formed, and a color filter layer for transmission is formed on the remaining portion to lower the concentration.

The color filter layer can be formed between the partition walls by discharging the coloring composition directly using an inkjet apparatus. It is also possible to form by using a conventional method of repeating pattern exposure and developing treatment after coating and forming a colored material. If necessary, an overcoat layer may be formed on the color filter layer. This is used in order to complement the performance of the color filter layer in terms of flatness, moisture resistance on the surface of resistance, chemical resistance and the like, and also to ensure barrier property for preventing elution from the color filter layer. As a material to be used, a transparent resin such as an acrylic copolymer or an epoxy resin composition containing a maleimide in a thermosetting type is preferable.

[Liquid crystal layer]

As the operation alignment method of the liquid crystal layer of the liquid crystal display device of the present invention, a twisted nematic (TN) method, an STN (super twisted nematic) method, an ECB (Electrically Controlled Birefringence) method, an IPS (MVA), Patterned Vertical Alignment (PVA), Optically Compensated Birefringence (OCB), Hybrid Aligned Nematic (HAN), and Axially Symmetric Aligned Microcell (ASM) , A halftone gray scale method, a domain division method, or a display method using a ferroelectric liquid crystal or an antiferroelectric liquid crystal. The driving method of the liquid crystal cell is not particularly limited. The liquid crystal cell is driven by a passive matrix method used in STN-LCD or the like, an active matrix method using active electrodes such as a TFT (Thin Film Transistor) electrode, a TFD (Thin Film Diode) A plasma addressing method, or the like. The tilt angle of the liquid crystal is large in the black display state than in the white display state, and the tilt angle of the liquid crystal in the liquid crystal display device of the present invention is larger than that of the back display state in the TN display mode, STN mode, ECB mode, VA mode, MVA mode, PVA mode, OCB mode, HAN mode, , And is more preferably used.

The liquid crystal display device of the present invention is not limited to the configurations shown in Figs. 1 and 2, and other members may be provided as long as the effects of the present invention are not impaired. A wide-band? / 4 plate can be used between the polarizing plate on the viewer side and the liquid crystal cell or between the polarizing plate on the backlight side and the liquid crystal cell for the purpose of converting circularly polarized light into linearly polarized light or linearly polarized light into circularly polarized light. One retardation plate may be used to achieve broadband characteristics, or two or more retardation plates may be appropriately combined with the retardation size or the slow axis angle. In addition, in order to achieve a wide band, an optical film having a small wavelength dispersibility is preferable as a retarder. As the material of the phase difference plate, specifically, a liquid crystal film or a polymer stretched film may be used. As the polymer stretched film, a stretched film such as a polymer material showing uniaxial or biaxial property such as polycarbonate (PC), polymethacrylate (PMMA), polyvinyl alcohol (PVA), norbornene polymer or the like can be used . For example, a uniaxially stretched film (manufactured by JSR Corporation) is preferable in that the wavelength dispersion is small. For example, in the combination direction of two or more sheets of retardation plates, the angle of the slow axis of the retarder having the phase difference of? / 2 and the slow axis of the retarder having the retardation of? / 4 is 60 占 and the phase difference is? / 4 The angle between the slow axis of the retardation plate and the polarization axis of the polarizing film (the direction in which the transmittance becomes maximum in the plane) is set to 75 占 and the angle between the slow axis of the retardation plate having the retardation of? / 2 and the polarizing axis of the polarizing film is set to 15 Thus, circularly polarized light, that is, a wide band? / 4 can be achieved in the entire visible region. An angle between the slow axis of the phase plate having the retardation of? / 4 and the slow axis of the second optically anisotropic layer is 60 占 and the angle between the slow axis of the retardation plate having the retardation of? / 4 and the polarization axis of the polarizing film is 15 degrees, and the angle between the slow axis of the retarder having the phase difference of? / 2 and the polarization axis of the polarizing film may be set to 75 deg. The allowable range of the angle is within ± 10 °, preferably within ± 8 °, more preferably within ± 6 °, more preferably within ± 5 °, even more preferably within ± 4 ° Do.

Example

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following embodiments.

[Preparation of Illustrative Compound (2)] [

According to the following scheme, Exemplified Compound (2) was prepared.

&Lt; EMI ID =

The synthesis of the compound (2-1) to the compound (2-3) was carried out by the method described in Journal of Chemical Crystallography (1997), 27 (9), p.515-526.

To 50 ml of a tetrahydrofuran solution of 8.5 g (0.1 mol) of cyanoacetic acid (2-4) and 14.4 g (0.1 mol) of 4-hydroxybutylacrylic acid ester (2-5) was added dicyclohexylcarbodiimide DCC) (20.6 g, 0.1 mol) was added dropwise under ice-cooling. The mixture was heated to room temperature and stirred for 2 hours as it was, and then the solid matter was removed by filtration. The solvent of the filtrate was removed under reduced pressure, and the resulting solid matter was further removed by filtration to obtain 18.6 g (yield: 88 mol%) of the compound (2-6).

N-methyl-2-pyrrolidone (NMP) was dissolved in 50 mg of Irganox 1010 (trade name, available from Ciba Specialty Chemicals), 15.7 g (50 mmol) of the compound (2-3), 12.7 g ) 100 mL of the suspension was heated to 80 DEG C under a nitrogen atmosphere. After the suspension solution became a homogeneous solution, it was cooled by stirring for 1.5 hours. Ethyl acetate and water were added to separate the layers, and the organic layer was washed with water, 0.5 N hydrochloric acid, and water in this order. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification was conducted by silica gel column chromatography to obtain 12.8 g of a compound (2-7) (yield: 65 mol%).

To a solution of 17.6 g (66 mmol) of the compound (2-8) in 20 ml of toluene was added 11.8 g (99 mmol) of thionyl chloride and a catalytic amount of N, N-dimethylformamide was added. The mixture was heated to 80 ° C and stirred for 2 hours. The solvent was distilled off. (THF) solution of 11.8 g (30 mmol) of the compound (2-7), 10 mg of Irganox 1010 (trade name, manufactured by Chiba Specialty Chemicals) and 7.1 g (90 mmol) of pyridine , And the mixture was dropped in a nitrogen atmosphere. After completion of dropwise addition, the mixture was stirred for 3 hours, and then stirred at room temperature for 1 hour. Ethyl acetate and water were added to separate the layers, and the organic layer was washed with water, 0.5 N hydrochloric acid, and water in this order. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification was conducted by silica gel column chromatography to obtain 20.0 g of the exemplified compound (2) (yield: 75 mol%).

&Lt; Identification data of Exemplified Compound (2) >

&Lt; Measurement of liquid crystal properties and optical properties of Exemplary Compound (2)

Example 2 (2) was observed under a heating polarizing microscope using an automatic melting point measuring device FP-900 and FP-82HT manufactured by Metrasara, and it was confirmed that this compound showed a nematic liquid crystal phase at 142 DEG C to 250 DEG C Respectively. In addition, it was confirmed that the nematic liquid crystal phase was observed in the temperature range of 250 ° C to 90 ° C during the temperature drop observation. The liquid crystal was injected into a wedge cell subjected to a parallel alignment treatment, an interference filter was inserted into the optical path, and the interval of the stripe was measured to calculate? N at each wavelength. The Δn at 150 ° C. was 0.033 at 450 nm, 0.042 at 550 nm, and 0.045 at 650 nm, and Δn (450 nm) / Δn (550 nm) was 0.79. That is, the exemplary compound (2) is a liquid crystal compound satisfying the above-mentioned formula (1).

The following liquid crystal compound (c) was prepared.

(25)

The liquid crystal compound (c)

The phase transition temperature of the liquid crystalline compound (c) exhibited a nematic (Ne) phase at a melting point of 51 ° C up to 60.7 ° C during the temperature raising process, an Ne phase at 60.7 ° C to 36.7 ° C at a temperature drop, (SmA) phase at &lt; RTI ID = 0.0 &gt; As a result of measuring the wavelength dispersion of? N at 40 占 폚 in the same manner as described above,? N (450 nm) /? N (550 nm) = 1.03. Namely, this liquid crystalline compound (c) is a liquid crystal compound which does not satisfy the above-mentioned formula (1) and Δn has a net dispersion wavelength dependency.

[Example 1: Preparation of optically anisotropic film]

A saponification treatment was applied to a commercially available cellulose acetate film (Fujitack TD80UF, manufactured by Fuji Film, Re = 3 nm, Rth = 45 nm), and a polyvinyl alcohol solution was applied and dried to rub the alignment film Respectively. 100 parts by mass of the exemplified compound (2), 0.1 part by mass of the exemplified compound (AE-3), 10 parts by mass of the liquid crystal compound (c), and a polymerization initiator (Irgacure 819, trade name, available from Ciba Specialty Chemicals) Was dissolved in 350 parts by mass of chloroform to prepare a thin film. When the liquid crystal composition was oriented at a temperature of 130 캜, it was uniformly oriented. Thereafter, ultraviolet rays of 400 mJ / cm 2 were irradiated in an atmosphere of nitrogen at 120 캜 to polymerize the liquid crystal compound, and the liquid crystal compound was cooled to fix the alignment state of the liquid crystal compound to form the optically anisotropic film (A-1). The thickness of the optically anisotropic film (A-1) was 4.5 占 퐉. Thus, a retardation film (1) as a laminate of the cellulose acylate film and the optically anisotropic film (A-1) was obtained.

The in-plane retardation (Re) at each wavelength was measured using an automatic birefringence meter (KOBRA-21ADH, trade name, manufactured by Ohji Instruments Co., Ltd.) Was 95 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, and 122 nm at a wavelength of 650 nm. The average inclination angle of the liquid crystal molecules in the optically anisotropic film (A-1) was measured by measuring the Re when the sample was inclined at ± 40 degrees with the fast axis as the rotation axis and subtracting the Re contribution of the cellulose acylate film previously measured The result was 36 degrees.

[Example 2: Preparation of optically anisotropic film]

A solution obtained by dissolving 100 parts by mass of Exemplary Compound (2), 0.1 part by mass of Exemplified Compound (AE-3) and 4 parts by mass of Polymerization Initiator (Irgacure 819) in 350 parts by mass of chloroform, And then applied to a polyether ether ketone film having a mid alignment film formed thereon to prepare a thin film. When the liquid crystal compound was oriented at a substrate temperature of 140 캜, it was uniformly oriented. Thereafter, ultraviolet rays of 400 mJ / cm 2 were irradiated in a nitrogen atmosphere to polymerize the liquid crystal compound, and the liquid crystal compound was cooled to form an optically anisotropic film (A-2) in which the alignment state of the liquid crystal compound was fixed. The thickness of the optically anisotropic film (A-2) was 4.70 탆.

The resulting optically anisotropic film (A-2) was transferred from a film onto a glass plate coated with a pressure-sensitive adhesive, and the film was measured using an automatic birefringence meter (KOBRA-21ADH, trade name, manufactured by Oji Instruments Co., Ltd.) Re at each wavelength was 94 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, and 123 nm at a wavelength of 650 nm. The Re was measured when the sample was tilted by +/- 40 degrees with the fast axis as the rotation axis, and the average inclination angle of the liquid crystal molecules in the optically anisotropic film (A-2) was calculated to be 36 degrees.

[Example 3: Preparation of ECB reflective transmission type liquid crystal display device]

&Lt; Production of optically anisotropic layer-integrated polarizing plate (A)

First, a polarizing membrane was prepared by adsorbing iodine on a stretched polyvinyl alcohol film, saponified on a commercially available cellulose acetate film (Fuji Tack TD80UF), and attached to one side of the polarizing membrane using a polyvinyl alcohol-based adhesive. The cellulose acetate film side of the retardation film (1) prepared in Example 1 was saponified and adhered to the other side of the polarizing film using a polyvinyl alcohol adhesive to form an optically anisotropic film-integrated polarizing plate (A) Respectively. At this time, the polarizing plate was bonded such that the angle between the slow axis direction of the optically anisotropic film (A-1) and the absorption axis of the polarizing layer was 45 degrees.

&Lt; Formation of liquid crystal display device &

An alignment film of polyimide was formed on a substrate having a transparent electrode film (thickness: 2000 ANGSTROM) formed on a color filter and a backlight side TFT formed with a reflective electrode and a transparent light region separately prepared thereon, and subjected to an anti- Respectively. Next, glass beads having a particle diameter of 4.1 탆 were dispersed. Then, a sealant of an epoxy resin containing spacer particles was printed at a position corresponding to the outer frame of the black matrix formed around the pixel group of the color filter, and the color filter substrate and the backlight side substrate were combined to produce a pressure of 10 kg / cm . Then, the bonded glass substrate was heat-treated at 150 DEG C for 90 minutes, and the sealing agent was cured to obtain a substrate laminate. This substrate laminate was degassed under vacuum, and then returned to the atmospheric pressure to inject a liquid crystal having a dielectric constant of +10 and DELTA n of 0.086 into the gap between the two glass substrates to obtain a liquid crystal cell of the ECB mode.

Two oriented norbornene retardation films having in-plane retardation (Re) of 550 nm and a retardation (Re) of 250 nm and 97 nm and a polarizing plate HLC2-2518 manufactured by Sanlit Co., Ltd. were laminated on the viewer side of this liquid crystal cell, . The order of the adhesion was as follows. First, a 97 nm retardation film was attached to a liquid crystal cell, then a retardation film of 250 nm was attached, and a polarizing plate was bonded thereon. The slow axis of the retardation film and the absorption axis orientation of the polarizing plate are set such that the retardation film of 97 nm is 49 degrees, the retardation film of 250 nm is 347 degrees, and the absorption axis of the polarizing plate is 151 Respectively. The liquid crystal alignment direction of the liquid crystal layer of the liquid crystal cell is 45 degrees. Next, the optically-anisotropic layer-integrated polarizing plate (A) was attached to the back-light side of the liquid crystal cell on the liquid crystal cell at an azeotropic azimuth angle of 225 degrees of the optically anisotropic film (A-1) to produce a liquid crystal panel. In this case, the average direction of the axis in which the director of the liquid crystal molecules in the liquid crystal layer at the time of black display is projected on the layer parallel plane and the direction in which the director of the aligned liquid crystal molecules in the optically anisotropic film (A-1) . However, the oblique direction of the aligned liquid crystal molecules in the optically anisotropic film (A-1) and the oblique direction of the liquid crystal molecules in the liquid crystal layer upon application of a voltage are different by 180 degrees.

Subsequently, as a cold cathode tube backlight for a color liquid crystal display apparatus, phosphors obtained by mixing BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn and LaPO ₄ : Ce and Tb in a weight ratio of 50:50 were mixed with green (G), Y ₂ O ₃ : Eu was changed to red (R), and BaMgAl ₁₀ O ₁₇ : Eu was changed to blue (B) to produce a white three-wavelength fluorescent lamp having an arbitrary hue. A liquid crystal panel provided with the above polarizing plate was provided on the backlight to prepare an ECB transflective liquid crystal display device-1.

[Example 4: Preparation of ECB reflective transmission type liquid crystal display device]

&Lt; Production of retardation film (B-1) (second optically anisotropic layer) >

A commercially available cellulose acetate film (Fuji Tack TD80UF) was saponified, and a polyvinyl alcohol solution was applied and dried to form an alignment film. Onto the above, 90 parts by mass of the following discotic liquid crystal compound, 10 parts by mass of the following monomer, 1 part by mass of the air interface side tilt angle reducing agent and 3 parts by mass of a polymerization initiator (Irgacure 819) were dissolved in 350 parts by mass of methyl ethyl ketone Was applied to a bar to prepare a thin film. When the liquid crystal composition was oriented at a temperature of 125 占 폚, homogeneous horizontal alignment was obtained. Thereafter, a retardation film (B-1) comprising an optically anisotropic layer and a cellulose acetate film, in which the liquid crystal compound was polymerized by irradiation with ultraviolet rays of 400 mJ / cm 2 at 100 ° C and cooled, .

(26)

Disc-shaped liquid crystal compound

(27)

Monomer

(28)

Air interface side tilt angle reducing agent

The retardation (Rth) in the thickness direction at each wavelength was measured using an automatic birefringence meter (KOBRA-21ADH, trade name, manufactured by Ohji Instruments Co., Ltd.) Was 137 nm at a wavelength of 450 nm and 129 nm at a wavelength of 550 nm, and Rth (450 nm) / Rth (550 nm) was 1.06. The in-plane retardation (Re) at a wavelength of 550 nm was 1 nm.

The polarizing plate HLC2-2518 manufactured by Sanlit Co., Ltd. was coated with a pressure-sensitive adhesive, and the optically anisotropic film (A-2) prepared in Example 2 was laminated on the polarizing plate HLC2-2518 of the optical anisotropic film (A- And the polyether ether ketone film of the support was peeled off. Next, a pressure-sensitive adhesive was coated thereon to adhere the retardation film (B-1).

An ECB transflective liquid crystal display-2 was produced in the same manner as in Example 3 except that this was used on the backlight side of the liquid crystal cell.

[Example 5]

A commercially available polyamic acid solution (SE-150, manufactured by Nissan Chemical Industries, Ltd.) was diluted with N-methylpyrrolidone so as to have a solid content concentration of 2% by mass and filtered with a polypropylene filter having a pore diameter of 30 탆 And used as a coating liquid for an orientation layer. The coating liquid for alignment layer obtained above is applied to the substrate SB provided with the separately prepared reflection electrode and the backlight side TFT on which the transmission light region is formed by using a piezo type head to form a droplet on the concave portion corresponding to the transmission portion, Dried, and then heated at 250 캜 for 60 minutes to form a backlight side substrate. The thickness of the orientation layer was 0.1 mu m. Subsequently, the formed alignment layer was rubbed.

The composition prepared in Example 1 was filtered with a polypropylene filter having a pore size of 0.2 탆 and a piezoelectric head was used to etch the concave portion of the substrate on which the alignment layer was formed. After the solvent was dried, it was aged at 130 캜 in a heating and drying orientation to form a layer having a uniform liquid crystal phase. Next, the temperature was lowered to 100 DEG C, and the hybrid alignment state was fixed by irradiating the layer with ultraviolet light (illuminance of 200 mW / cm &lt; 2 &gt; and irradiation dose of 800 mJ / cm &lt; 2 &gt;) under a nitrogen atmosphere with an oxygen concentration of 0.3% To form an optically anisotropic film (A-3).

The adjustment of the retardation corresponding to each pixel of R, G and B was carried out by changing the thickness of the retardation layer formed by controlling the proper amount of the liquid crystal composition coating liquid.

The retardation and the average tilt angle of the formed optically anisotropic film (A-3) were measured by a parallel Nicol method using a microscopic spectrometer, and the front retardation (Re) at a wavelength (?) Corresponding to R, G, And the retardation (Re) when the sample was tilted by +/- 40 degrees with the slow axis as the rotation axis were measured and calculated. The in-plane retardation (Re) of the optically anisotropic film (A-3) was 94 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, and 135 nm at a wavelength of 650 nm. The average inclination angle was 36 degrees in any area.

The reflective transmissive liquid crystal display device-3 was formed in the same manner as in Example 3 except that the substrate thus produced was used as a backlight side substrate. At this time, no polarizing plate was formed between the backlight side substrate and the polarizing plate, and the polarizing plate HLC2-2518 was directly attached using a pressure-sensitive adhesive. The angle between the absorption axis of this polarizing plate and the liquid crystal alignment axis in the liquid crystal cell was 45 degrees.

[Example 6]

The following liquid crystal compound (d) was prepared. The following liquid crystal compound (d) can be synthesized in the same manner as in the synthesis of the above exemplified compound (2) except that the reagent to be used is changed.

[Chemical Formula 29]

The phase transition temperature of the liquid crystalline compound (d) had a melting point of 119 占 폚 and exhibited a nematic phase up to 153 占 폚 during the temperature raising process and an Ne phase at 153 占 폚 to 80 占 폚 during the temperature lowering test. In the same manner as described above, the wavelength dispersion of? N was measured at 103 占 폚 and? N (450 nm) /? N (550 nm) = 0.85. That is, this liquid crystalline compound (d) is a liquid crystal compound satisfying the above formula (1).

100 parts by mass of the liquid crystalline compound (d), 0.1 part by mass of the exemplified compound (AE-3), 0.5 by mass of the exemplified compound (PE-4), and 4 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) And 200 parts by mass of methyl ethyl ketone was applied to the substrate to prepare a thin film. An optically anisotropic film (A-4) was produced in the same manner as in Example 1, except that the liquid crystal composition was oriented at a temperature of 120 占 폚 and then irradiated with ultraviolet rays of 400 mJ / cm2 at 90 占 폚 in a nitrogen atmosphere to polymerize the liquid crystal compound ). The thickness of the optically anisotropic film (A-4) was 4.8 mu m.

The in-plane retardation (Re) at each wavelength of the prepared optically anisotropic film (A-4) was measured in the same manner as described above. As a result, it was found to be 98 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, And was 122 nm at a wavelength of 650 nm. The average inclination angle of the liquid crystal molecules in the optically anisotropic film (A-4) was calculated in the same manner as described above, and found to be 37 degrees.

An ECB transflective liquid crystal display-4 was produced in the same manner as in Example 3 except that the optically anisotropic film (A-4) was used instead of the optically anisotropic film (A-1).

[Example 7]

The following liquid crystal compound (e) was prepared. The following liquid crystal compound (e) can be synthesized in the same manner as in the synthesis of the above exemplified compound (2) except that the reagent to be used is changed.

(30)

The phase transition temperature of the liquid crystalline compound (e) had a melting point of 147 占 폚 and exhibited a nematic phase up to 163 占 폚 during the heating step and a Ne phase of 163 占 폚 to 100 占 폚 during the temperature observation. As a result of measuring the wavelength dispersion of? N at 113 占 폚 in the same manner as described above,? N (450 nm) /? N (550 nm) = 0.86. That is, this liquid crystal compound (e) is a liquid crystal compound satisfying the above formula (1).

100 parts by mass of the liquid crystalline compound (e), 0.1 part by mass of Exemplified Compound (AE-3), 0.5 by mass of Exemplified Compound (PE-4) and 4 parts by mass of polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) Was dissolved in 200 parts by mass of methyl ethyl ketone to prepare a thin film. An optically anisotropic film (A-2) was obtained in the same manner as in Example 2 except that the liquid crystal composition was oriented at a temperature of 130 占 폚 and then irradiated with ultraviolet rays of 400 mJ / cm2 at 100 占 폚 in a nitrogen atmosphere to polymerize the liquid crystal compound. 5). The thickness of the optically anisotropic film (A-5) was 4.60 mu m.

The Re in each wavelength of the prepared optically anisotropic film (A-5) was measured in the same manner as described above. As a result, it was found that 98 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, 123 Nm. The average tilt angle of the liquid crystal molecules in the optically anisotropic film (A-5) was calculated in the same manner as described above, and was found to be 35 degrees.

An ECB transflective liquid crystal display device-5 was produced in the same manner as in Example 4 except that the optically anisotropic film (A-5) was used instead of the optically anisotropic film (A-2).

[Example 8]

An optically anisotropic film (A-6) was formed in the same manner as in Example 5 except that the composition prepared in Example 6 was used.

The in-plane retardation (Re) of the formed optically anisotropic film (A-6) was measured in the same manner as described above. As a result, it was 98 nm at a wavelength of 450 nm, 114 nm at a wavelength of 550 nm, 135 Nm. Further, the average inclination angle of the liquid crystal molecules in the optically anisotropic film (A-6) was calculated in the same manner as described above, and as a result, all regions were 37 degrees.

The thus fabricated substrate was used as a backlight-side substrate, and a reflective transmissive liquid crystal display device-6 was formed in the same manner as in Example 5.

(Evaluation of Liquid Crystal Display)

The transmission luminance of the produced reflective transmission type liquid crystal display devices -1 to 6 was measured using a spectroscopic radiation luminance meter under a dark room. At this time, the viewing angle was fixed horizontally with the liquid crystal display device horizontally, and the polar angle was fixed at 10 degrees in the normal direction in the range of 0 to 60 degrees, and the azimuth angle of the liquid crystal display device was changed every 10 degrees at each angle The luminance was measured at ON and OFF of the liquid crystal display device, and the contrast ratio, which is the ratio of the luminance at ON and OFF, was calculated. The sum of the contrast ratios at all polar angles and azimuths was added to the total azimuth, and an average value obtained by dividing the sum by 211 of the total number of measurement points was obtained. The larger the average value, the larger the contrast ratio at a wide viewing angle. By using this index, it is possible to evaluate the viewing angle characteristics of the display device over a wide viewing angle.

The liquid crystal display devices -1 to 6 were 93, 110, 120, 94, 111, and 122, respectively.

[Comparative Example 1]

A liquid crystal display device was manufactured in the same manner as in Example 3. [ However, in Comparative Example 1, instead of using the retardation film (1) having the optically anisotropic film (A-1), a wide-band? / 4 plate produced by superposing two conventional stretched films on the backlight side Of the polarizing plate and the substrate. Each of the Re and the azimuth angles of the slow axes at 550 nm of the two stretched films had a Re of 99 nm from the side close to the liquid crystal cell, a retardation azimuth angle of 212 deg. And Re of 250 nm and a retardation azimuth angle 107 °, and HLC2-2518 was attached to the polarizing plate on the backlight side so that its absorption axis was in the 43 ° direction.

In this liquid crystal display device, the average value of the contrast was as low as 21 in the above evaluation method.

[Comparative Example 2]

A liquid crystal display device was manufactured in the same manner as in Example 3. [ However, in Comparative Example 2, the retardation film (1) having the optically anisotropic film (A-1) was not used and the optically anisotropic layer (C) formed by the following method was used as the? / 4 layer The stretched film was disposed between the polarizing plate on the backlight side and the substrate using a? / 2 layer, and was formed into a configuration used in a conventional liquid crystal display device. The azimuthal angle of the slow axis of the lambda / 4 layer formed on the side close to the liquid crystal cell is 212 degrees, and the azimuth angles of the retardation and the slow axis at 550 nm of the lambda / 2 layer are 250 nm and 107 deg. HLC2-2518 was attached to the polarizing plate so that its absorption axis was in the direction of 43 degrees.

&Lt; Formation of optically anisotropic layer (C)

100 parts by mass of the following rod-shaped liquid crystal compound, 0.1 part by mass of Exemplified Compound (AE-3), and 100 parts by mass of a polymerization initiator (manufactured by Fuji Photo Film Co., Ltd.) were laminated on a support on which polyvinyl alcohol was formed as an orientation film on a cellulose acetate film (IRGACURE 819) dissolved in 350 parts by mass of methyl ethyl ketone was applied to the substrate by applying a bar, and then irradiated with ultraviolet rays of 400 mJ / cm 2 at 90 ° C. The front surface Re of this anisotropic layer was 109 nm at 450 nm and 98 nm at 550 nm, and the average inclination angle was 35 degrees. Further, the rod-shaped liquid crystal compound described below is a compound in which? N exhibits a net dispersion wavelength dependency in a visible light range.

(31)

Similarly, the liquid crystal display device was evaluated by the above evaluation method, and the average value of the contrast was 79.

[Comparative Example 3]

A liquid crystal display device was produced in the same procedure as in Example 3 except that the optically anisotropic film (D-1) was formed in the following manner instead of forming the optically anisotropic film (A-1).

&Lt; Formation of optically anisotropic film (D) >

First, a commercially available cellulose acetate film (Fuji Tack TD80UF) was subjected to a saponification treatment, a polyvinyl alcohol solution was applied and dried, and the alignment film thus formed was subjected to rubbing treatment. 100 parts by mass of the exemplified compound (2), 0.5 part by mass of the air interface side tilt angle reducing agent, 10 parts by mass of the liquid crystal compound (c), and 100 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) ) Was dissolved in 350 parts by mass of chloroform to prepare a thin film. When the liquid crystal composition was oriented at a temperature of 130 캜, it was uniformly oriented. Thereafter, ultraviolet rays of 400 mJ / cm 2 were irradiated in a nitrogen atmosphere at 120 캜 to polymerize the liquid crystal compound, and the liquid crystal compound was cooled to form an optically anisotropic layer (D) in which the alignment state of the liquid crystal compound was fixed.

Re of the prepared film (optically anisotropic layer (D)) was 95 nm at a wavelength of 450 nm, 113 nm at a wavelength of 550 nm, and 122 nm at a wavelength of 650 nm, and the average inclination angle was 1 deg.

As a result of evaluating the liquid crystal display device using the above evaluation method, the average value of the contrast was as low as 21.

1 is a schematic cross-sectional view of an example of a liquid crystal display device of the present invention.

2 is a schematic cross-sectional view of another example of the liquid crystal display device of the present invention.

Explanation of symbols

1. The viewer's polarizer

2. Phase difference film

3. Substrate

4. Transmissive color filter

5. Reflective color filter

6. Black Matrix

7. Overcoat layer

8. Liquid crystal layer

9. Reflector

10. Substrate

11. The retardation film

12. Backlight side polarizer

13. Optically anisotropic layer (B)

14. An optically anisotropic layer (A)

Claims (14)

An optically anisotropic film containing at least one kind of liquid crystal compound which expresses a nematic phase or a Smectic phase and whose birefringence? N (?) At a wavelength (?) Of the liquid crystal phase satisfies the following formula (1) Wherein molecules of the liquid crystal compound in the anisotropic film are fixed in an oblique alignment state, An optical anisotropic film having retardation (Re) in a plane of 80 to 160 nm at a wavelength of 550 nm: (1)? N (450 nm) /? N (550 nm) <1. The method according to claim 1, Wherein an angle of inclination of a molecule of the liquid crystal compound is different from an upper surface and a lower surface of the optically anisotropic film, and an average inclination angle of molecules of the liquid crystal compound is from 5 degrees to 85 degrees. The method according to claim 1, Wherein an angle of inclination of the molecules of the liquid crystal compound is the same on an upper surface and a lower surface of the optically anisotropic film, and an average inclination angle of molecules of the liquid crystal compound is 5 degrees to 85 degrees. The method according to claim 1, Wherein the liquid crystal compound is a compound represented by the following general formula (I): optically anisotropic film: [Chemical Formula 1] The compound of formula (I)

Wherein A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -NR- (R represents a hydrogen atom or a substituent), -S-, and -CO-; Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16 and forms a 5 or 6-membered ring together with the described CC = CC or C = CC = C in the formula ; R ¹ , R ² and R ³ each independently represent a substituent; m is an integer of 0 to 4; L ¹ and L ² each independently represent a single bond or a divalent linking group; X represents a nonmetal atom of Groups 14 to 16, wherein X may be a hydrogen atom or a substituent R ⁴ ; At least one of R, R ¹ , R ² , R ³ and R ⁴ has a polymerizable group. 5. The method of claim 4, Wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II): optically anisotropic film: (2) In general formula (II)

In the formulas, A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -NR- (R represents a hydrogen atom or a substituent), -S-, and -CO-; Z represents one or two atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16 and forms a 5 or 6-membered ring together with the described CC = CC or C = CC = C in the formula ; R ¹ , R ² , and R ³ each independently represent a substituent; m is an integer of 0 to 4; L ¹ and L ² each independently represent a single bond or a divalent linking group; R ⁵ and R ⁶ each independently represents a substituent, and at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ has a polymerizable group. delete The method according to claim 1, An optically anisotropic film formed by exposing a fluid containing at least the liquid crystal compound to a surface from an ink jet type ejection head to form a liquid crystal phase and then exposing the liquid crystal phase. An optical element comprising: a first optically anisotropic layer made of an optically anisotropic film according to any one of claims 1 to 5; a backlight; a polarizing layer; a pair of substrates; and a liquid crystal layer And a liquid crystal cell having a reflective portion and a transmissive portion. 9. The method of claim 8, And the first optically-anisotropic layer is disposed between the polarizing layer and the pair of substrates. 9. The method of claim 8, And the first optically anisotropic layer is disposed between the pair of substrates. 10. The method of claim 9, A second optically anisotropic layer having a retardation (Rth) in the thickness direction at a wavelength of 550 nm of 40 nm to 150 nm and an in-plane retardation (Re) of 0 nm to 20 nm at a wavelength of 550 nm is added And the second optically anisotropic layer is disposed at a position between the liquid crystal layer and the first optically anisotropic layer or at a position where the liquid crystal layer sandwiches the first optically-anisotropic layer. 12. The method of claim 11, And Rth of the second optically-anisotropic layer exhibits a forward scatter wavelength dependence in a visible light range. 9. The method of claim 8, Wherein the liquid crystal layer is a liquid crystal layer having a larger tilt angle of liquid crystal in a black display state than a white display state. 9. The method of claim 8, An average direction of the axis of the director of the liquid crystal molecules in the liquid crystal layer at the time of black display is projected on the layer parallel plane and a direction in which the director of the molecule of the liquid crystal compound in the first optically anisotropic layer is projected on the layer parallel plane, Device.

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